Optical systems fabricated by printing-based assembly

ABSTRACT

Provided are optical devices and systems fabricated, at least in part, via printing-based assembly and integration of device components. In specific embodiments the present invention provides light emitting systems, light collecting systems, light sensing systems and photovoltaic systems comprising printable semiconductor elements, including large area, high performance macroelectronic devices. Optical systems of the present invention comprise semiconductor elements assembled, organized and/or integrated with other device components via printing techniques that exhibit performance characteristics and functionality comparable to single crystalline semiconductor based devices fabricated using conventional high temperature processing methods. Optical systems of the present invention have device geometries and configurations, such as form factors, component densities, and component positions, accessed by printing that provide a range of useful device functionalities. Optical systems of the present invention include devices and device arrays exhibiting a range of useful physical and mechanical properties including flexibility, shapeability, conformability and stretchablity.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.13/100,774, filed May 4, 2011, which is a continuation of U.S. patentapplication Ser. No. 11/981,380, filed Oct. 31, 2007, which claimspriority under 35 U.S.C. 119(e) to U.S. Provisional Patent Applications60/885,306 filed Jan. 17, 2007 and 60/944,611 filed Jun. 18, 2007, eachof which are hereby incorporated by reference in their entirety to theextent not inconsistent with the disclosure herein.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made, at least in part, with United Statesgovernmental support under DEFG02-91-ER45439 awarded by U.S. Departmentof Energy. The United States Government has certain rights in thisinvention.

BACKGROUND OF INVENTION

Since the first demonstration of a printed, all polymer transistor in1994, a great deal of interest has been directed at development of a newclass of electronic systems comprising flexible integrated electronicdevices on plastic substrates. [Garnier, F., Hajlaoui, R., Yassar, A.and Srivastava, P., Science, Vol. 265, pgs 1684-1686] Substantialresearch has been directed over the last decade toward developing newsolution processable materials for conductors, dielectrics andsemiconductors elements for flexible polymer-based electronic devices.Progress in the field of flexible electronics is not only driven by thedevelopment of new solution processable materials but also by new devicegeometries, techniques for high resolution, dense patterning of largesubstrate areas, and high throughput processing strategies compatiblewith plastic substrates. It is expected that the continued developmentof new materials, device configurations and fabrication methods willplay an essential role in the rapidly emerging new class of flexibleintegrated electronic devices, systems and circuits.

Interest in the field of flexible electronics arises out of severalimportant advantages provided by this technology. First, the mechanicalruggedness of plastic substrates provides a platform for electronicdevices less susceptible to damage and/or electronic performancedegradation caused by mechanical stress. Second, the inherentflexibility and deformability of plastic substrate materials allowsthese materials to be integrated into useful shapes, form factors andconfigurations not possible with conventional brittle silicon basedelectronic devices. For example, device fabrication on flexible,shapeable and/or bendable plastic substrates has potential to enable aclass of functional devices having revolutionary functionalcapabilities, such as electronic paper, wearable computers, large-areasensors and high resolution displays, that are not feasible usingestablished silicon-based technologies. Finally, electronic deviceassembly on flexible plastic substrates has potential for low costcommercial implementation via high speed processing techniques, such asprinting, capable of assembling electronic devices over large substrateareas.

Despite considerable motivation to develop a commercially feasibleplatform for flexible electronics, the design and fabrication offlexible electronic devices exhibiting good electronic performancecontinues to present a number of significant technical challenges.First, conventional well-developed methods of making single crystallinesilicon based electronic devices are incompatible with most plasticmaterials. For example, traditional high quality inorganic semiconductorcomponents, such as single crystalline silicon or germaniumsemiconductors, are typically processed by growing thin films attemperatures (>1000 degrees Celsius) that significantly exceed themelting or decomposition temperatures of most or all plastic substrates.In addition, many inorganic semiconductors are not intrinsically solublein convenient solvents that would allow for solution based processingand delivery. Second, although amorphous silicon, organic or hybridorganic-inorganic semiconductors have been developed that are compatiblewith low temperature processing and integration into plastic substrates,these materials do not exhibit electronic properties comparable toconventional single crystalline semiconductor based systems.Accordingly, the performance of electronic devices made from thesealternative semiconductor materials is less than current state of theart high performance semiconductor devices. As a result of theselimitations, flexible electronic systems are presently limited tospecific applications not requiring high performance, such as use inswitching elements for active matrix flat panel displays withnon-emissive pixels and in light emitting diodes.

Macroelectronics is a rapidly expanding area of technology which hasgenerated considerable interest in developing commercially feasibleflexible electronic systems and processing strategies. The field ofmacroelectronics relates to microelectronic systems whereinmicroelectronic devices and device arrays are distributed and integratedon large area substrates significantly exceeding the physical dimensionsof conventional semiconductor wafers. A number of macroelectronicproducts have been successfully commercialized including large areamacroelectronic flat panel display products. The majority of thesedisplay systems comprise amorphous or polycrystalline silicon thin filmtransistor arrays patterned onto rigid glass substrates. Macroelectronicdisplay devices having substrate dimensions as large as 100's of meterssquared have been achieved. Other macroelectronic products indevelopment include photovoltaic device arrays, large area sensors andRFID technology.

Despite considerable progress in this field, there is continuedmotivation to integrate flexible substrates and device structures intomacroelectronic systems so as to impart new device functionality, suchas enhanced ruggedness, mechanical flexibility and bendability. Toaddress this need, a number material strategies for flexiblemacroelectronic systems are currently being pursued including organicsemiconductor thin film transistor technology, nano-wire andnanoparticle based flexible electronics and organic/inorganicsemiconductor hybrid technology. In addition, substantial research iscurrently directed at developing new fabrication processes for accessinghigh throughput and low cost manufacturing of macroelectronic systems.

U.S. patent Ser. No. 11/145,574 and Ser. No. 11/145,542, both filed onJun. 2, 2005, disclose a high yield fabrication platform using printablesemiconductor elements for making electronic devices, optoelectronicdevices and other functional electronic assemblies by versatile, lowcost and high area printing techniques. The disclosed methods andcompositions provide for the transfer, assembly and/or and integrationof microsized and/or nanosized semiconductor elements using dry transfercontact printing and/or solution printing techniques providing goodplacement accuracy, registration and pattern fidelity over largesubstrate areas. The disclosed methods provide important processingadvantages enabling the integration of high quality semiconductormaterials fabricated using conventional high temperature processingmethods onto substrates by printing techniques which may beindependently carried out at relatively low temperatures (<about 400degrees Celsius) compatible with a range of useful substrate materials,including flexible plastic substrates. Flexible thin film transistorsfabricated using printable semiconductor materials exhibit goodelectronic performance characteristics, such as device field effectmobilities greater than 300 cm² V⁻¹ s⁻¹ and on/off ratios greater than10³, when in flexed and non-flexed conformations.

It will be appreciated from the foregoing that a need exists for methodsof making large area integrated electronics, including macroelectronicsystems. In particularly, fabrication methods for these systems areneeded that are capable of high-throughput and low cost implementation.Further, there is currently a need for macroelectronic systems combininggood electronic device performance and enhanced mechanical functionalitysuch as flexibility, shapeability, bendability and/or stretchability.

SUMMARY OF THE INVENTION

The present invention provides optical devices and systems fabricated,at least in part, via printing-based assembly and integration ofprintable functional materials and/or semiconductor-based devices anddevice components. In specific embodiments the present inventionprovides light emitting systems, light collecting systems, light sensingsystems and photovoltaic systems comprising printable semiconductorelements, including large area, high performance macroelectronicdevices. Optical systems of the present invention comprise printablesemiconductor containing structures (e.g., printable semiconductorelements) assembled, organized and/or integrated with other devicecomponents via printing techniques that exhibit performancecharacteristics and functionality comparable to single crystallinesemiconductor based devices fabricated using conventional hightemperature processing methods. Optical systems of the present inventionhave device geometries and configurations, such as form factors,component densities, and component positions, accessed by printing thatprovide a range of useful device functionalities. Optical systems of thepresent invention include devices and device arrays exhibiting a rangeof useful physical and mechanical properties including flexibility,shapeability, conformability and/or stretchablity. Optical systems ofthe present invention include, however, devices and device arraysprovided on conventional rigid or semi-rigid substrates, in addition todevices and device arrays provided on flexible, shapeable and/orstretchable substrates.

This invention also provides device fabrication and processing steps,methods and materials strategies for making optical systems at least inpart via printing techniques, including contact printing, for exampleusing a conformable transfer devices, such as an elastomeric transferdevice (e.g., elastomer layer or stamp). In specific embodiments,methods of the present invention provide a high-throughput, low costfabrication platform for making a range of high performance opticalsystems, including light emitting systems, light collecting systems,light sensing systems and photovoltaic systems. Processing provided bythe present methods is compatible with large area substrates, such asdevice substrates for microelectronic devices, arrays and systems, andis useful for fabrication applications requiring patterning of layeredmaterials, such as patterning printable structures and/or thin filmlayers for electronic and electro-optic devices. Methods of the presentinvention are complementary to conventional microfabrication andnanofabrication platforms, and can be effectively integrated intoexisting photolithographic, etching and thin film deposition devicepatterning strategies, systems and infrastructure. The present devicefabrication methods provide a number of advantages over conventionalfabrication platforms including the ability to integrate very highquality semiconductor materials, such as single crystallinesemiconductors and semiconductor-based electronic devices/devicecomponents, into optical systems provided on large area substrates,polymer device substrates, and substrates having contoured aconformation.

In an aspect, the present invention provides processing methods usinghigh quality bulk semiconductor wafer starting materials that areprocessed to provide large yields of printable semiconductor elementswith preselected physical dimensions and shapes that may be subsequentlytransferred, assembled and integrated into optical systems via printing.An advantage provided by the present printing-based device fabricationmethods is that the printable semiconductor elements retain desirableelectronic properties, optical properties and compositions of the highquality bulk wafer starting material (e.g., mobility, purity and dopingetc.) while having different mechanical properties (e.g., flexibility,stretchability etc.) that are useful for target applications such asflexible electronics. In addition, use of printing-based assembly andintegration, for example via contact printing or solution printing, iscompatible with device fabrication over large areas, including areasgreatly exceeding the dimensions of the bulk wafer starting material.This aspect of the present invention is particularly attractive forapplications in macroelectronics. Further, the present semiconductorprocessing and device assembly methods provide for very efficient use ofvirtually the entire starting semiconductor material for makingprintable semiconductor elements that can be assembled and integratedinto a large number of devices or device components. This aspect of thepresent invention is advantageous because very little of the highquality semiconductor wafer starting material is wasted or discardedduring processing, thereby providing a processing platform capable oflow cost fabrication of optical systems.

In one aspect, the present invention provides optical systems comprisingprintable semiconductor elements, including printablesemiconductor-based electronic devices/device components, assembled,organized and/or integrated using contact printing. In an embodiment ofthis aspect, the invention provides a semiconductor-based optical systemmade by a method comprising the steps of: (i) providing a devicesubstrate having a receiving surface; and (ii) assembling one or moreplurality of printable semiconductor elements on the receiving surfaceof the substrate via contact printing. In an embodiment, the opticalsystem of this aspect of the present invention comprises an array ofsemiconductor-based devices or device components assembled on thereceiving surface of the substrate via contact printing. In specificembodiments, each of the printable semiconductor elements of the opticalsystem comprises a semiconductor structure having a length selected fromthe range of 0.0001 millimeters to 1000 millimeters, a width selectedfrom the range of 0.0001 millimeters to 1000 millimeters and a thicknessselected from the range of 0.00001 millimeters to 3 millimeters. In anembodiment of this aspect, printable semiconductor elements comprise onor more semiconductor devices selected from the group consisting of LED,solar cell, diode, p-n junctions, photovoltaic systems,semiconductor-based sensor, laser, transistor and photodiode, having alength selected from the range of 0.0001 millimeters to 1000millimeters, a width selected from the range of 0.0001 millimeters to1000 millimeters and a thickness selected from the range of 0.00001millimeters to 3 millimeters. In an embodiment, the printablesemiconductor element comprises a semiconductor structure having alength selected from the range of 0.02 millimeters to 30 millimeters,and a width selected from the range of 0.02 millimeters to 30millimeters, preferably for some applications a length selected from therange of 0.1 millimeters to 1 millimeter, and a width selected from therange of 0.1 millimeters to 1 millimeter, preferably for someapplications a length selected from the range of 1 millimeters to 10millimeters, and a width selected from the range of 1 millimeter to 10millimeters. In an embodiment, the printable semiconductor elementcomprises a semiconductor structure having a thickness selected from therange of 0.0003 millimeters to 0.3 millimeters, preferably for someapplications a thickness selected from the range of 0.002 millimeters to0.02 millimeters. In an embodiment, the printable semiconductor elementcomprises a semiconductor structure having a length selected from therange of 100 nanometers to 1000 microns, a width selected from the rangeof 100 nanometers to 1000 microns and a thickness selected from therange of 10 nanometers to 1000 microns.

In an embodiment, the printable semiconductor element(s) is/are anelectronic device or a component of an electronic device. In anembodiment, the printable semiconductor element(s) is/are selected fromthe group consisting of: an LED, a laser, a solar cell, a sensor, adiode, a transistor, and a photodiode. In an embodiment, the printablesemiconductor element(s) comprises the semiconductor structureintegrated with at least one additional structure selected from thegroup consisting of: another semiconductor structure; a dielectricstructure; conductive structure, and an optical structure. In anembodiment, the printable semiconductor element comprises thesemiconductor structure integrated with at least one electronic devicecomponent selected from the group consisting of: an electrode, adielectric layer, an optical coating, a metal contact pad and asemiconductor channel. In an embodiment, the system further comprises anelectrically conducting grid or mesh provided in electrical contact withat least a portion of said printable semiconductor elements, wherein theelectrically conducting grid or mesh providing at least one electrodefor said system.

Useful contact printing methods for assembling, organizing and/orintegrating printable semiconductor elements of this aspect include drytransfer contact printing, microcontact or nanocontact printing,microtransfer or nanotransfer printing and self assembly assistedprinting. Use of contact printing is beneficial in the present opticalsystems because it allows assembly and integration of a plurality ofprintable semiconductor in selected orientations and positions relativeto each other. Contact printing in the present invention also enableseffective transfer, assembly and integration of diverse classes ofmaterials and structures, including semiconductors (e.g., inorganicsemiconductors, single crystalline semiconductors, organicsemiconductors, carbon nanomaterials etc.), dielectrics, and conductors.Contact printing methods of the present invention optionally providehigh precision registered transfer and assembly of printablesemiconductor elements in preselected positions and spatial orientationsrelative to one or more device components prepatterned on a devicesubstrate. Contact printing is also compatible with a wide range ofsubstrate types, including conventional rigid or semi-rigid substratessuch as glasses, ceramics and metals, and substrates having physical andmechanical properties attractive for specific applications, such asflexible substrates, bendable substrates, shapeable substrates,conformable substrates and/or stretchable substrates. Contact printingassembly of printable semiconductor structures is compatible, forexample, with low temperature processing (e.g., less than or equal to298K). This attribute allows the present optical systems to beimplemented using a range of substrate materials including those thatdecompose or degrade at high temperatures, such as polymer and plasticsubstrates. Contact printing transfer, assembly and integration ofdevice elements is also beneficial because it can be implemented via lowcost and high-throughput printing techniques and systems, such asroll-to-roll printing and flexographic printing methods and systems. Thepresent invention include methods wherein contact printing is carriedout using a conformable transfer device, such as an elastomeric transferdevice capable of establishing conformal contact with external surfacesof printable semiconductor elements. In embodiments useful for somedevice fabrication applications contact printing is carried out using anelastomeric stamp.

In an embodiment, the step of contact printing-based assembly ofprintable semiconductor comprises the steps of: (i) providing aconformable transfer device having one or more contact surfaces; (ii)establishing conformal contact between an external surface of theprintable semiconductor element and the contact surface of theconformable transfer device, wherein the conformal contact bonds theprintable semiconductor element to the contact surface; (iii) contactingthe printable semiconductor element bonded to the contact surface andthe receiving surface of the device substrate; and (iv) separating theprintable semiconductor element and the contact surface of theconformable transfer device, thereby assembling the printablesemiconductor element on the receiving surface of the device substrate.In some embodiments, the step of contacting the printable semiconductorelement bonded to the contact surface and the receiving surface of thedevice substrate comprises establishing conformal contact between thecontact surface of the transfer device having the printablesemiconductor element(s) and the receiving surface. In some embodiments,the printable semiconductor element(s) on the contact surface arebrought into contact with an adhesive and/or planarizing layer providedon the receiving surface to facilitate release and assembly on thedevice substrate. Use of elastomeric transfer devices, such as elastomerlayers or stamps including PDMS stamps and layers, is useful in somemethods given the ability of these devices to establish conformalcontact with printable semiconductor elements, and the receivingsurfaces, external surface and internal surfaces of device substratesand optical components.

Use of printable semiconductor materials and printablesemiconductor-based electronic devices/device components in embodimentsof this aspect provides the capable of integrating a range of highquality semiconductor materials for fabricating optical systemsexhibiting excellent device performance and functionality. Usefulprintable semiconductor elements include, semiconductor elements derivedfrom high quality semiconductor wafer sources, including singlecrystalline semiconductors, polycrystalline semiconductors, and dopedsemiconductors. In a system of the present invention, the printablesemiconductor element comprises a unitary inorganic semiconductorstructure. In a system of the present invention, the printablesemiconductor element comprises a single crystalline semiconductormaterial. In addition, use of printable semiconductor structuresprovides the capability of integrating printable structures comprisingsemiconductor electronic, optical and opto-electronic devices, devicecomponents and/or semiconductor heterostructures, such as hybridmaterials made via high temperature processing and subsequentlyassembled on a substrate via printing. In certain embodiment, printablesemiconductor elements of the present invention comprise functionalelectronic devices or device components, such as p-n junctions,semiconductor diodes, light emitting diodes, semiconductor lasers (e.g.,Vertical-Cavity Surface-Emitting Lasers (VCSEL)), and/or photovoltaiccells.

In an embodiment, the printable semiconductor elements are assembled onsaid device substrate such that they generate a multilayer structure onsaid receiving surface. In an embodiment, for example, the multilayerstructure comprises mechanically-stacked solar cells. In an embodiment,for example, the printable semiconductor elements are solar cells havingdifferent band-gaps.

Optical systems of this aspect of the present invention may optionallycomprise a variety of additional device elements including, but notlimited to, optical components, dielectric structures, conductivestructures, adhesive layers or structures, connecting structures,encapsulating structures, planarizing structures, electro-optic elementsand/or thin film structures and arrays of these structures. In anembodiment, for example, an optical system of the present inventionfurther comprises one or more passive or active optical componentsselected from the group consisting of: collecting optics, concentratingoptics, diffusing optics, dispersive optics, optical fibers and arraysthereof, lenses and arrays thereof, diffusers, reflectors, Braggreflectors, waveguides (“light-pipes”), and optical coatings (e.g.,reflective coatings or antireflective coatings). In some embodiments,active and/or passive optical components are spatially aligned withrespect to at least one of the printable semiconductor elements providedon the device substrate. Optical systems of this aspect of the presentinvention may optionally comprise a variety of additional devicecomponents including, but not limited to, electrical interconnects,electrodes, insulators and electro-optical elements. Printed-basedassembly may be used to assembly and integrate additional deviceelements and additional device components, in addition to assembly andintegration of these additional elements by variety of techniques wellknown in the field of microelectronics, including but not limited to,optical photolithography, deposition techniques (e.g., chemical vapordeposition, physical vapor deposition, atomic layer deposition,sputtering deposition etc.), soft lithography, spin coating and laserablation patterning.

Printing-based assembly provides a very high degree of control over thephysical dimensions, geometry, relative spatial orientation andorganization, doping levels and materials purity of the printablesemiconductor elements assembled and integrated into the present opticalsystems. In an embodiment, printable semiconductor elements of theoptical system are provided on the receiving surface of the substratewith a density equal to or greater than 5 semiconductor elements mm⁻¹,preferably for some embodiments a density equal to or greater than 50semiconductor elements mm⁻¹, and preferably for some applications adensity equal to or greater than 100 semiconductor elements mm⁻¹. Inanother embodiment, the printable semiconductor elements of the opticalsystem have at least one longitudinal physical dimension (e.g., length,width etc.), optionally two longitudinal physical dimensions, less thanor equal to 2000 nanometers, and in some embodiments less than or equalto 500 nanometers. In another embodiment, each printable semiconductorelement of the optical system has at least one cross-sectional physicaldimension (e.g. thickness) less than or equal to 100 microns, preferablyfor some applications less than or equal to 10 microns, and preferablyfor some applications less than or equal to 1 microns. In anotherembodiment, the positions of the printable semiconductor elements in theoptical system relative to each other are selected to within 10,000nanometers.

Printable semiconductor elements may be assembled in selectedorientations with respect to each other or other device elements ofoptical systems of the present invention. In an embodiment, printablesemiconductor elements of the optical system are longitudinal alignedwith respect to each other. The present invention includes, for example,optical systems wherein printable semiconductor elements extend lengthsthat are parallel to within 3 degrees of each other. In anotherembodiment, the optical system further comprising first and secondelectrodes provided on the receiving surface, wherein the printablesemiconductor elements are in electrical contact with at least one ofthe electrodes, and wherein the printable semiconductor elements providea fill factor between the first and second electrodes greater than orequal to 10%, preferably for some embodiments equal to or larger than50%.

The present invention also includes optical systems comprising printablesemiconductor elements arranged in a low density (or sparse)configuration. Use of a low density configuration has benefits for someapplications, as the amount of semiconductor incorporated in the deviceis low, thus, accessing lower costs. In these configurations,semiconductor elements may be arrange on a substrate so that the densityof semiconductor elements is low enough such that the system isoptically transparent, preferably for some embodiments more than 50%optical transparent at selected wavelength. In an embodiment, printablesemiconductor elements of the optical system are provided on thereceiving surface of the substrate with a density equal to or less than1000 semiconductor elements mm⁻¹, preferably for some embodiments adensity equal to or less than 500 semiconductor elements mm⁻¹, and morepreferably for some embodiments a density equal to or less than 50semiconductor elements mm⁻¹. In an embodiment of the present methods andsystems capable of accessing sparse configurations, the semiconductorelements cover less than or equal to 10% of the receiving surface of thetarget substrate; in another embodiment less than or equal to 1%; and inanother embodiment less than or equal to 0.1%. In another embodiment,the optical system further comprising first and second electrodesprovided on the receiving surface, wherein the printable semiconductorelements are in electrical contact with at least one of the electrodes,and wherein the printable semiconductor elements provide a fill factorbetween the first and second electrodes less than or equal to 10%,preferably for some embodiments less than or equal to 5%.

The present invention includes optical systems comprising printablesemiconductor elements assembled and integrated onto a range of usefulsubstrate materials, including glass substrates, polymer substrate,plastic substrates, metal substrates, ceramic substrates, wafersubstrates, and composite substrates. Substrates useful in the presentoptical systems include those having useful mechanical and/or physicalproperties such as flexibility, shapeability, stretchability, mechanicalruggedness and optical transparency at selected wavelengths. In someembodiments, optical systems of the present invention comprise printablesemiconductor elements assembled and integrated onto a device substrateprepatterned with device components. In some embodiment, optical systemsof the present invention comprise printable semiconductor elementsassembled and integrated onto a device substrate having a selectedoptically functionality, such as a device substrate comprising a lens,lens array, optical window, reflector, optical coating, series ofoptical coatings, or optically transparent substrate optionally havingone or more optical coatings such as reflective coatings orantireflective coatings. In some embodiments, optical systems of thepresent invention comprise printable semiconductor elements assembledand integrated onto a device substrate having a contoured receivingsurface, such as a concave receiving surface, convex receiving surface,a spherical surface, an elliptical surface or receiving surface having acomplex contour with both concave regions and convex regions.

Optical systems of the present invention may further comprise one ormore encapsulating layers, planarizing layers, laminating layers, coverlayers and/or bonding layers. Encapsulating layers, laminating layers,planarizing layers, covering layers or bonding layers may be provided ontop of printable semiconductor elements or other device components toprovide enhanced mechanical stability and ruggedness. Encapsulatinglayers, laminating layers, planarizing layers, covering layers orbonding layers may be provided in a configuration so as to mechanically,optically and/or electrically interconnect device components andstructures of the present optical systems. Encapsulating layers,laminating layers, covering layers, planarizing layers, or bondinglayers may comprise layers of deposited material, spin coated layersand/or molded layers. Encapsulating layers, laminating layers, coveringlayers, planarizing layers, or bonding layers are preferably at leastpartially optically transparent for some optical systems andapplications of the present invention. Useful encapsulating layers,laminating layers, planarizing layers, covering layers and/or bondinglayers may comprise one or more polymers, composite polymers, metals,dielectric materials, epoxy materials or prepolymer materials. In anembodiment, printable semiconductor elements are bonded or otherwiseintegrated to the receiving surface via one or more of the following:(i) cold welding the semiconductor elements to the receiving surface viaa metal layer provided between the printable semiconductor elements andthe receiving layer; (ii) provided via an adhesive layer providedbetween the printable semiconductor elements and the receiving layer; or(iii) provided by a lamination, encapsulation or planarizing layerprovided on top of the printable semiconductor elements and thereceiving layer. If the adhesive layer is metal, this layer can alsoserve to establish electrical contact to the printable semiconductorelement during printing-based assembly and integration.

In some embodiments, the composition and thickness of an encapsulating,laminating or planarizing layer is selected such that the printablesemiconductor elements, such as printed semiconductor devices and/ordevice components, assembled on a device substrate are placed near or onthe neutral mechanical plane. In an embodiment, for example anencapsulating or laminating layer is provided on top of assembledprintable semiconductor elements, wherein the encapsulating orlaminating layer has a composition and thickness similar to that of thedevice substrate. In these embodiments, matching the encapsulatingand/or laminating layer composition and thickness dimension with that ofthe device substrate results in the printable semiconductor elementsresiding near the neutral mechanical plane. Alternatively, the thicknessand Young's modulus of the encapsulating and/or laminating layer may beselected to result in the printable semiconductor elements residing nearthe neutral mechanical plane. An advantage of processing methods anddevice geometries wherein printable semiconductor elements reside nearthe neutral mechanical plane of the device is that strain on theseelements are minimized during bending or deformation. This strategy formanaging strains generated during bending has benefits for minimizingdelamination or other degradation of the device result from bendinginduced strain.

In some embodiments, optical systems of the present invention providelight emitting optical systems, including, but not limited to, advancedlighting systems, arrays of light emitting diodes, arrays ofsemiconductor lasers (e.g., VCSELs), passive matrix LED (light emittingdiode) displays, active matrix LED displays, ILED (inorganic lightemitting diode) displays, macroelectronic display devices, and flatpanel displays. In some embodiments, optical systems of the presentinvention provide light sensing optical systems including, opticalsensors and sensor arrays, flexible sensors, stretchable sensors,conformal sensors and sensor skins. In some embodiments, optical systemsof the present invention provide optical systems providing both lightemitting and light sensing functionality such as sheet scanners. Opticalsystems of the present invention include energy conversion and storagesystems including photovoltaic devices, device arrays and systemsincluding solar cell arrays. In some embodiments, optical systems of thepresent invention comprise a plurality of one or more LEDs, photovoltaiccells, semiconductor lasers, photodiodes, and electro-optical elementshaving at least two physical dimensions (e.g., length, width, diameteror thickness) less than 200 microns. In an embodiment, for example, thepresent invention provides an optical system comprising an array ofsolar cells, wherein each cell in the array has at least two physicaldimensions (e.g., length, width, diameter or thickness) less than 200microns. In another embodiment, for example, the present inventionprovides an optical system comprising an array of LEDs, wherein each LEDin the array has a thickness less than 3 microns, and preferably forsome applications less than 1 micron.

In another aspect, the present invention provides a method for making anoptical system comprising the steps: (i) providing a device substratehaving a receiving surface; and (ii) assembling one or more printablesemiconductor elements on the receiving surface of the substrate viacontact printing; wherein each of the printable semiconductor elementscomprise a semiconductor structure having a length selected from therange of 0.0001 millimeters to 1000 millimeters, a width selected fromthe range of 0.0001 millimeters to 1000 millimeters and a thicknessselected from the range of 0.00001 millimeters to 3 millimeters. In anembodiment, the printable semiconductor element comprises asemiconductor structure having a length selected from the range of 0.02millimeters to 30 millimeters, and a width selected from the range of0.02 millimeters to 30 millimeters, preferably for some applications alength selected from the range of 0.1 millimeters to 1 millimeter, and awidth selected from the range of 0.1 millimeters to 1 millimeter,preferably for some applications a length selected from the range of 1millimeters to 10 millimeters, and a width selected from the range of 1millimeter to 10 millimeters. In an embodiment, the printablesemiconductor element comprises a semiconductor structure having athickness selected from the range of 0.0003 millimeters to 0.3millimeters, preferably for some applications a thickness selected fromthe range of 0.002 millimeters to 0.02 millimeters. In an embodiment,the printable semiconductor element comprises a semiconductor structurehaving a length selected from the range of 100 nanometers to 1000microns, a width selected from the range of 100 nanometers to 1000microns and a thickness selected from the range of 10 nanometers to 1000microns.

Useful contact printing methods useful in this aspect of the presentinvention include dry transfer contact printing, microcontact ornanocontact printing, microtransfer or nanotransfer printing and selfassembly assisted printing. Optionally, methods of the present inventionemploy contact printing as implemented using a conformable transferdevice, such as an elastomeric transfer device (e.g., elastomeric stamp,composite stamp or layer). Optionally, a plurality of printablesemiconductor elements are assembled on the receiving surface of thesubstrate, for example in a dense or spares configuration. Optionally,methods of this aspect of the present invention further comprise thestep of prepatterning the device substrate with one or more devicecomponents. Optionally, methods of this aspect of the present inventionfurther comprise the step of providing one or more optical components inoptical communication or optical registration with the printablesemiconductor elements. In a method of the present invention, theprintable semiconductor element comprises a unitary inorganicsemiconductor structure. In a method of the present invention, theprintable semiconductor element comprises a single crystallinesemiconductor material.

Optionally, methods of the present invention include the step ofproviding a laminating layer, such as a polymer or elastomer layer ontop of at least a portion of the printable semiconductor elementsassembled on the receiving surface of the substrate. Optionally, methodsof the present invention include the step of planarizing at least aportion of the printable semiconductor elements assembled on thereceiving surface of the substrate. Optionally, methods of the presentinvention include the steps of: (i) providing a planarizing layer to thereceiving surface and (ii) embedding at least a portion of the printablesemiconductor elements in the planarizing layer. Optionally, methods ofthe present invention include the step of patterning one or moreelectrical contacts, electrodes, contact pads or other electricalinterconnect structures on at least a portion of the printablesemiconductor elements.

Methods of this aspect of the present invention further comprise thestep of assembling and/or integrating one or more additional devicecomponents onto the device substrate, such as optical components,electronic components and/or electro-optical components. Assemblingand/or integrating additional device components in the present methodscan be implemented in combination with a large number of otherfabrication techniques, including, but not limited to, lithographicpatterning (e.g., optical lithograph and soft lithography), depositiontechniques (e.g., CVD, PVD, ALD, etc.), laser ablation patterning,molding techniques (e.g., replica molding), spin coating, self assembly,contact printing, and solution printing. In some embodiments, otherprocessing techniques, such as plasma treatment, etching, metallizationand cold welding are used to generate, assemble or integrate devicecomponents, including printable semiconductor elements.

In an embodiment, for example, a combination of optical lithography anddeposition techniques are used to pattern the device substrate prior toor after printing-based assembly of the printable semiconductorelements. In another embodiment, for example, replica molding is used togenerate optical components, such as a lens array or diffusers, whichare subsequently patterned with printable semiconductor elements viacontact printing. In another embodiment, for example, printablesemiconductor elements provided on a device substrate are electricallyconnected to electrodes and electrical interconnects patterned on thedevice substrate using a combination of optical lithography anddeposition techniques. In another embodiment, for example, an opticalsystem comprising a multilayer structure is generated by repeatedtransfer and assembly steps of printable semiconductor elements, such asthin film transistors, LEDs, semiconductor lasers and/or photovoltaicdevices, printed on the device substrate, optionally in combination withadditional processing carried out via spin coating, deposition andencapsulation/planarizing steps for integrating additional devicecomponents, such as electrode, interconnects, adhesive layers,lamination layers, optical components and encapsulation or planarizinglayers.

In an embodiment, the method of this aspect further comprises the stepof providing one or more optical components in optical communication oroptical registration with the printable semiconductor elements, forexample optical components selected from the group consisting of:collecting optics, diffusing optics, dispersive optics, optical fibersand arrays thereof, lenses and arrays thereof, diffusers, reflectors,Bragg reflectors, and optical coatings (e.g., reflective coatings orantireflective coatings). For example, methods of the present inventionmay optionally include the step of providing an array of opticalcomponents in optical communication or optical registration with atleast a portion of the printable semiconductor elements. In someembodiments, an optical component of the array is individually addressedto each of the printable semiconductor elements. In a specificembodiment, the array of optical components is fabricated via replicamolding; wherein the printable semiconductor elements are assembled on areceiving surface of the array of optical components via contactprinting.

In an embodiment, a method of the present invention further comprisesproviding one or more electrodes in electrical contact with theprintable semiconductor elements provided on the device substrate. In anembodiment electrodes are defined and integrated into optical systemsusing a combination of optical lithographic patterning and depositiontechniques (e.g., thermal deposition, chemical vapor deposition orphysical vapor deposition). In another embodiment, electrodes areassemble and interconnected with devices elements using printing.

Methods of the present invention are useful for providing opticalsystems on large areas of a receiving surface of a substrate. In anembodiment useful for making large array optical systems, printablesemiconductor elements are provided on an area of the receivingsubstrate selected over the range of 0.05 m² to 10 meters², andpreferably for some applications selected over the range of 0.05 m² to 1meters²

In an embodiment, the present methods further comprise the step ofproviding an adhesive layer to the receiving surface prior to theassembling step. Adhesive layers are useful in the present invention forbonding or otherwise affixing printable semiconductor elements and otherdevice elements to the receiving surface of the substrate. Usefuladhesive layers include but are not limited to one or more metal layersor a polymer layers. In an embodiment, the present methods furthercomprise the step of providing a laminating, planarizing orencapsulating layer on the printable semiconductor elements. Laminating,planarizing or encapsulating layers are useful in the present methodsfor at least partially encapsulating or laminating printablesemiconductor elements and other elements on the receiving surface.

Optionally, the method of the present invention further comprises thesteps of: (i) providing an inorganic semiconductor wafer; (ii)generating the plurality of printable semiconductor elements from thesemiconductor wafer; and (iii) transferring the plurality of printablesemiconductor elements from the wafer to the receiving surface viacontact printing, thereby assembling the plurality of printablesemiconductor elements on the receiving surface of the substrate. In anembodiment, the plurality of printable semiconductor elements areassembled on the receiving surface of the substrate and on the receivingsurfaces of one or more additional substrates, wherein the plurality ofprintable semiconductor elements assembled on the substrates comprisesat least 5% to 50% by mass of the semiconductor wafer. This aspect ofthe present invention is beneficial because it provides for veryefficient use of the semiconductor wafer starting material resulting inlow cost fabrication of optical systems. In some embodiments, the“plurality of printable semiconductor elements assembled on thesubstrates” may comprise a very low fraction (<about 5% by mass or area)of the final, device substrate. In other words, the printed systems mayexhibit a low fill-factor of the semiconductor. The advantage of alow-fill factor is that it requires a small amount of semiconductormaterial, which in these cases is expensive on a per-area basis, topopulate large areas of final, device substrate(s).

In another embodiment, the present invention provides a method of makinga semiconductor-based optical system comprising the steps of: (i)providing an optical component having an external surface and aninternal surface; (ii) providing a electrically conducting grid or meshon the internal surface of the optical component; (iii) providing adevice substrate having a receiving surface; (iv) assembling a pluralityof printable semiconductor elements on the receiving surface of thesubstrate via contact printing; wherein each of the printablesemiconductor elements comprise a unitary inorganic semiconductorstructure having a length selected from the range of 0.0001 millimetersto 1000 millimeters, a width selected from the range of 0.0001millimeters to 1000 millimeters and a thickness selected from the rangeof 0.00001 millimeters to 3 millimeters; and (v) transferring theoptical component having the grid or mesh to the substrate, wherein theoptical component is positioned on top of the semiconductor elementsassembled on the on the receiving surface of the substrate, and whereinthe grid or mesh is provided between the optical component and thesemiconductor elements. In an embodiment, the printable semiconductorelement comprises a semiconductor structure having a length selectedfrom the range of 0.02 millimeters to 30 millimeters, and a widthselected from the range of 0.02 millimeters to 30 millimeters,preferably for some applications a length selected from the range of 0.1millimeters to 1 millimeter, and a width selected from the range of 0.1millimeters to 1 millimeter, preferably for some applications a lengthselected from the range of 1 millimeters to 10 millimeters, and a widthselected from the range of 1 millimeter to 10 millimeters. In anembodiment, the printable semiconductor element comprises asemiconductor structure having a thickness selected from the range of0.0003 millimeters to 0.3 millimeters, preferably for some applicationsa thickness selected from the range of 0.002 millimeters to 0.02millimeters. In an embodiment, the printable semiconductor elementcomprises a semiconductor structure having a length selected from therange of 100 nanometers to 1000 microns, a width selected from the rangeof 100 nanometers to 1000 microns and a thickness selected from therange of 10 nanometers to 1000 microns.

In a method of the present invention, the printable semiconductorelement comprises a unitary inorganic semiconductor structure. In amethod of the present invention, the printable semiconductor elementcomprises a single crystalline semiconductor material.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1. provides a schematic showing optical systems provided by thepresent invention. As shown in FIG. 1, the present invention provides anumber of classes of optical systems and related methods of making thesesystems, including systems for light generation and systems for lightharvesting comprising printed inorganic optoelectronic systems withintegrated optical components in registry.

FIG. 2 A-E provides schematic diagrams of optical systems of the presentinvention comprising printable semiconductor elements. FIG. 2A shows aprinted LED array with integrated optical diffuser. FIG. 2B shows aVCSEL array on a silicon chip with integrated optical fibers. FIG. 2Cshows a printed photovoltaic array with integrated optical collectors.FIG. 2D shows an artificial eye sensor comprising a printed photodiodearray on a collecting lens. FIG. 2E shows a sheet scanner having bothlight sensing and light generation functionality and comprising aprinted array LED and photodiode components and integrated collectionoptics provided on a polymer or other low cost substrate.

FIG. 3 provides a process flow schematic for the fabrication of a singlepixel element of a printed inorganic active matrix LED display of thepresent invention.

FIG. 4 provides a schematic illustration (not to scale) of a printedactive matrix LED display on a glass substrate. The display showncomprises 100 pixels and is an approximately 11 inch display. Thin filmtransistor (TFT) elements, LED elements, gate lines, anode lines anddata lines of the device are indicated in FIG. 4.

FIG. 5 provides photographs (FIG. 5A) and operating current-voltagecharacteristics (FIG. 5B) of a single pixel of an active matrix LEDdisplay on a (transparent) glass substrate. As shown in FIG. 5A thesingle pixel of an active matrix LED display comprises a printed TFTstructure, a LED structure, gate electrode and electrical interconnects.FIG. 5B provides a plot of current (A) verses drive bias (V) for thesingle pixel of an active matrix LED display.

FIG. 6 provides photographs of a 64 pixel active matrix LED display on a(transparent) glass substrate. FIG. 6A provides a photograph of a 64pixel partial LED display (Note: missing top contacts) comprising 1 mmtransistors printed on to the device substrate and ILEDs manually placedon the substrate. In the device shown in FIG. 6A pixels are provided ata 4 mm pitch. FIG. 6B provides a photograph of a printed silicon TFTwith interdigitated channel (thin green line) for high-currentoperation. FIG. 6C provides a photograph of two pixels illuminated byplacing a transparent common anode electrical contact against the LEDs.

FIG. 7A provides a process flow schematic for the fabrication of asingle pixel element of a printed inorganic passive matrix LED display.

FIG. 7B provides a process flow schematic for establishing electricalcontact by compression of a (soft) substrate/layer.

FIG. 8 provides a schematic illustration (not to scale) of a printedpassive matrix printed inorganic LED display. As shown in FIG. 8 thedisplay comprises a bottom substrate, electrode network, printed ILED,PDMS layer and top substrate.

FIG. 9 provides photographs of passively addressed printed inorganic LEDdisplays/arrays on glass and flexible PET substrates.

FIG. 10 provides a process flow schematic for printing inorganic lightemitters and collectors via cold-weld bonding techniques.

FIG. 11 provides a process flow schematic for printing using a donorcartridge and cold-weld bonding technique. In this method a cartridge ispatterned with SU-8. ILED structures are placed on the patterned surfaceof the cartridge. A stamp is used to take up the ILED structures andsubsequently print the ILED structures on a substrate prepatterned withelectrodes via transfer printing. The bottom panel of FIG. 11 shows anexample of a LED structure printed using this method.

FIG. 12 provides a schematic of an optical system of the presentinvention wherein diffusing optics are integrated with printable LEDstructures. In this embodiment, PDMS is molded on rough polystyrene. Acomparison of panels (a) and (b) show the affect of incorporation of adiffuser in this optical system. The diffuser can be a rough molded PDMSstructure. This figure demonstrates that diffusers can effectivelyincrease the size of the luminous region.

FIG. 13 provides a schematic of diffusing optics comprising radialdensity gradient scattering centers useful for LED lighting systems ofthe present invention. As shown in this Figures a printed LED structureunder metal is provided in optical communication with a plurality ofoptical scattering centers. The bottom panel in FIG. 13 shows a crosssectional view of scattering centers comprising relief features in atransparent substrate.

FIG. 14A provides an exemplary epilayer structure for the fabrication ofprintable micro-LEDs. As shown in this figure, the epilayer structurecomprises a series of device layers, sacrificial layers and a handlewafer. Individual layers in the epilayer structure are shown in thebottom panel of FIG. 14A. FIG. 14B provides an exemplary epilayerstructure for the fabrication of printable micro-LEDs comprising quantumwell emissive layers. The epilayer structure comprises a series ofsemiconductor layers provided between p-cladding and n-cladding layers.Specific compositions of each layer in the epilayer structure areprovided. FIG. 14C provides a table indicating the composition,thickness, doping and functionality of each layer in the epilayerstructure for the fabrication of printable micro-LEDs. FIG. 14Dillustrates an example of a mother wafer from which printable p-on-nGaAs solar cells may be produced by photolithography and etching layers9 through 4 and selectively removing layer 3 by a wet chemical etch.FIG. 14E illustrates provides another example of a mother wafer fromwhich printable n-on-p GaAs solar cells may be produced byphotolithography and etching layers 9 through 4 and selectively removinglayer 3 by a wet chemical etch.

FIG. 15 provides schematic diagrams illustrating the imperceptiblepixilation/high degree of transparency from low fill-factor, micro-sized(<˜100 micron footprint) LEDs. As shown in the top panel of this figure,the optical system comprises: (i) a first glass coated ITO or a low-fillfactor metal mesh layer; (ii) printed micro LEDS structures; and (iii) asecond glass coated ITO or a low-fill factor metal mesh layer. Top viewsare provided corresponding to the off state and the on state. Amagnification of the top view is also provided showing the positioningof micro LED structures.

FIG. 16 provides schemes for the release of printable light-emittinginorganic semiconductor micro-elements: micro-LEDs or VCSELs. Scheme 1describes the release of such elements by encapsulating them in apolymer, e.g. photoresist, and releasing them from the wafer on whichthey were grown by selectively etching an Al_(x)Ga_(1-x)As (x>about 70%)sacrificial layer using hydrofluoric acid. Scheme 2 describes release byencapsulating them in a conformal dielectric (e.g. silicon nitride) andreleasing them from the wafer by selectively oxidizing the AlGaAs andetching the oxidized material using aqueous potassium hydroxide. Scheme3 describes release by encapsulating them with a polymer, e.g.photoresist, followed by selective etching of a buried GaAs sacrificiallayer using an aqueous mixture of citric acid and hydrogen peroxide. Inscheme 3, the AlGaAs protects the underside of the light emittingelement from the citric acid-based etchant.

FIG. 17A provides a schematic process flow diagram illustratingfabrication of integrated solar cell/collector arrays by printing solarcells. FIG. 17B provides a schematic process flow diagram illustratingfabrication of integrated solar cell/collector arrays viainterconnection of registry of an optical array. FIG. 17C provides aschematic process flow diagram illustrating the operation of theintegrated solar cell/collector arrays.

FIG. 18A provides a schematic ray diagram (not to scale) showingoperation of the integrated low-level collecting optics (lens) andsolar-cell arrays of an optical system of the present invention. Asshown in FIG. 18A radiation is collected by the concentrator and focusedon printed microsolar cells. FIG. 18B shows an expanded view of amicrocell of the present invention comprising an antireflection layer,top contact and p-n junction.

FIG. 19 provide a schematic diagram illustration of light harvesting viareduction of semiconductor materials costs in a sheet-like form factor.The collector size is approximately 2 mm, the solar cell size isapproximately 0.1 mm, and the area multiplication (ratio of collectorarea and solar cell area) is approximately 400. As demonstrated by thecalculation show in this figures 1 ft² of processed semiconductor waferresults in approximately 400 ft² of light-harvesting area. Thiscalculation demonstrates the methods and optical systems of the presentinvention provide a high efficiency and low cost fabrication strategyfor high performance photovoltaic devices and systems.

FIG. 20 provides a schematic diagram of a collecting optic andheterogenously composed solar cell of a solar cell array(sympevolent/diventegration) of the present invention. As shown in thisfigure, collecting optics are provided in optical communication with anitride/phosophide and/or arsenide solar cell and silicon solar cellassembled on the device substrate via contact printing. FIG. 20 alsoprovides ray diagram of the incident light shown collection and focusfunctionality of a concentrator and individually addressed solar cells.Single crystal multilayer solar cells (i.e. third generation solarcells) are typically grown by MOCVD and are constrained by the necessityof crystal lattice mismatch between layers. In our system differentabsorbing layers can have arbitrary lattices and the materials selectedfor optimal spectrum absorption for each layer.

FIG. 21 provides a schematic process flow diagram for fabrication of anintegrated solar cell and lens array using a combination of replicamolding methods and contact printing. As shown in this figure a masterlens array is used to generate a negative replica mold, for example viareplica molding or imprinting techniques. Next, the molded PDMS layer isused to generate a plano-concave polymer lens array by casting thepolymer against the negative replica. As shown in FIG. 21, solar cellsprinted onto a device substrate are provided in optical communicationwith the lens array so as to generate an optical system of the presentinvention.

FIG. 22 demonstrates the ability of Fresnel lenses, a type ofconcentrating/collecting optic, to focus light to a small area for usein light harvesting systems described by the present invention. Fresnellens arrays can be used as optical concentrators due to its advantageousfeatures such as thin form factor and light weight compared withconventional lenses. The figure shows a focal area measurement forspherical and cylindrical Fresnel lenses.

FIG. 23 provides a schematic diagram illustrating an optical system ofthe present invention wherein horizontal light pipes and/or waveguidesare provided for light harvesting. This optical system uses transparent,structured media of appropriate index of refraction to capture normally-or obliquely-incident light and guide it in the plane of the substrateto a solar cell or solar cell array.

FIG. 24 provides a schematic showing an exemplary printable siliconsolar cell fabricated using a silicon on insulator SOI wafer. The solarcell comprises a doped top surface with a P/As mixture and is supportedby a buried oxide layer of the SOI wafer. FIG. 24 shows the solar cellmultilayer structure comprising a n⁺-Si (P/As) layer and p-Si(B) layer.

FIG. 25 provides a schematic process flow diagram illustrating a methodof transferring a printable solar cell to substrate using contactprinting and subsequent cold welding processing to affix the solar cellto a device substrate.

FIG. 26 provides a schematic diagram (not to scale) showing a top view(in parallel) of an exemplary configuration for top contacts to solararrays of the present invention. Microsolar cells (shown in gray) havingwidths of approximately 120 microns and lengths of approximately 1millimeter are provided in an array format on a device substrate. Metalfeatures are provided having widths of 60 microns and length on theorder of 1 inch. The metal features provide the top contacts of a solarcell device array of the present invention. This figures shows aflexible strip light made of blue LEDs and a thin kapton substrate witha bending radius equal to 0.85 cm.

FIG. 27 provides a schematic diagram of an “artificial eye” sensor ofthe current invention. The sensor comprises inorganic photodiode arraysdistributed on a lens having spherical curvature. Various lens shapesand angles are shown in FIG. 27

FIG. 28 provides a schematic diagram illustrating wrapping a planarsheet around a spherical surface demonstrating the necessity ofstretchability in an exemplary “artificial eye” sensor. As shown in FIG.28, conformal positioning of the planar sheet requires some degree ofstretchability to avoid failure.

FIG. 29 provide a schematic processes flow diagram showing a method formaking a microsolar cell array of the present invention.

FIG. 30. Estimated Short Circuit Current (J_(SC)) and AM1.5 Efficiencyas a function of Silicon Thickness.

FIG. 31. Scanning Electron Micrographs Showing Sequential Formation ofSi Multilayer Ribbon Stacks.

FIG. 32 provides a schematic diagram of a connection scheme where the Siribbons comprising p-type silicon with a thin n-type layer on top toform the emitter. Left side shows the as-transferred Si Ribbons, rightshows the connection (direct-write or screen-printing). Only four SiRibbons are shown for clarity.

FIG. 33 provides a schematic of a solar cell array of the presentinvention using PDMS for concentrating solar illumination.

FIG. 34. provides images showing results of printing single crystalsilicon onto plastic, glass, Si wafers, InP wafers and thin film a-Si.The microstamping process of the present invention is compatible with awide range of substrates.

FIG. 35 shows a schematic illustration of an exemplary process of thepresent invention, as applied to the printing of printable inorganicsemiconductor-based LEDs.

FIG. 36 provides an image and a schematic illustration of a printeruseful in the present methods of fabricating conformable LED lightingsystems.

FIG. 37 provides images of square (part a) and linear (part b) lightingdevices that comprise passively addressed blue inorganic LEDs assembledon plastic substrates via contact printing. The device in part (b)represents a conformal ILED-based thin film lighting device of thepresent invention.

FIG. 38 provides a schematic process flow diagram of a method offabricating a conformable LED lighting system of the present invention.

FIG. 39 provides a process flow diagram for fabricating an ILED lightdevice of the present invention comprising a flexible strip.

FIG. 40 provides a cross sectional view of a conformal ILED lightingsystem of the present invention comprising top and bottom PET substrates(approximately 175 microns thick), ILEDS structures (approximately 100microns thick), electrodes and a PDMS encapsulating coating.

FIG. 41 provides images of ILED lighting systems of the presentinvention in an unbent state, a first bent sate with a bending radius of7 cm, a second bent sate with a bending radius of 5 cm, third bent satewith a bending radius of 4.5 cm, a fourth bent sate with a bendingradius of 3 cm and in a state upon release of the bending stress. Theimages in FIG. 42 confirm that conformal ILED lighting systems of thepresent invention provide useful optical properties in bentconfigurations.

FIG. 42 provides an image of a flexible strip light made of blue LEDsand thin kapton substrates with bending radius equal to 0.85 cm.

FIG. 43 provides schematics showing two methods for assembling ILEDstructures on the device substrate.

FIG. 44 provides a schematic for the formation of a micro single crystalsilicon solar cell with low-level concentrating lens. In the first step(a) the micro structures are transferred from PDMS onto an embeddedelectrode which serves as the back electrical contact for the device.The silicon is transferred by laminating the PDMS onto the electrodesurface and slowly peeling the PDMS back. Next, in step (b),planarization followed by the formation of the top metal contacts isperformed. The device is completed by integrating a low concentrationcylindrical lens array made from PDMS onto the device (step c). In thisfinal step it can be seen that the device was designed such that therows of silicon cells align with the focal point of the lens array.

FIG. 45 provides images of a silicon solar cell transferred to a glasssubstrate. (a) Optical image of a single cell on a glass substrate withboth top and bottom electrical contacts. (b) current voltagecharacteristics—Typical I-V response for a device shown in (a) under AM1.5.

FIG. 46 provides images of a solar cell array joined to cylindricalcollecting optics. (a) Picture of the final fully integrated device withcylindrical lens array. (b) Picture of the same device without theincorporation of the lens array.

FIG. 47 provides a schematic diagram for generating optical concentratorarrays with integrated metal contacts onto mS-Silicon solar cells(micro-silicon solar cells). The process starts off with retrieval of ametal mesh pattern from a substrate (shown dark blue) via a PDMS moldedlens array. The lens array/mesh pattern can then be laminated inregistry onto an array of silicon solar cells.

FIG. 48 illustrates the process flow for generating solar cells andintegrated concentrating optics.

FIG. 49 provides images of a micro solar cell array printed onto goldbus lines on glass substrates via a thin PDMS adhesive layer. Also shownare current-voltage characteristics for the solar cell array.

FIG. 50 provides a schematic illustration of microcells of (a)vertical-type, (b) transverse-type, (c) combination of both types.

FIG. 51 provides a schematic diagram illustrating a method of thepresent invention for making large area optical systems usingmicromanipulation via transfer printing. This techniques provides formassively parallel assembly of inorganic semiconductor elements andsemiconductor devices having micro-sized and/or nanosized physicaldimensions.

FIG. 52 provide a plot of current (A) versus applied voltage (V) for ainorganic LED device assembled via transfer printing.

FIG. 53A provide a plot of current (A) versus applied voltage (V) for aprinted thin-film inorganic LED device assembled on a plastic substratevia transfer printing. FIG. 53A also provide a schematic diagram of theassembled device. FIG. 53B provides a schematic diagram shown anexemplary ILED epilayer structure useful in the present invention.

FIGS. 54A and 54B provides schematic diagrams of systems of the presentinvention comprising planarized printable semiconductor elements.

FIG. 55 provides a flow diagram illustrating processing steps in methodsof the present invention for making semiconductor-based optical systemscomprising planarized printable semiconductor elements, such asprintable semiconductor-based electronic devices and device components.

FIG. 56 provides experimental results characterizing the impact of stepedges on establishing electrical contact to and/or between printablesemiconductor elements.

FIG. 57 provides a process flow diagram for making printablesemiconductor elements comprising vertical solar cells that can besubsequently assembled and interconnected to fabricate a solar cellarray.

FIG. 58 provides SEM images of microsolar cells of different thicknessesfabricated from bulk wafers. (Top to bottom: 8 microns, 16 microns, 22microns thick).

FIG. 59 provides a plot showing IV characteristics of an individualsolar cell device fabricated using the present processing platform.

FIG. 60 shows processing for generating top contacts for the verticalsolar cells and related electronic performance data.

FIG. 61 provides a schematic showing a solar cell layout of transversetype solar cells to be patterned on a <111>p-type Si wafer and capableof subsequent assembly and integration via contact printing.

FIG. 62 provides a schematic showing the doping scheme wherein boron(P+) and phosphorous (n+) doped regions are patterned on the externalsurface of the patterned semiconductor ribbons.

FIG. 63 provides an overview schematic showing the process flow for cellpatterning and doping steps.

FIG. 64 provides a schematic diagram showing processing steps forpatterning solar cell ribbons illustrating photolithography and STS deepRIE etching process steps.

FIG. 65 shows results from KOH refining processing of the sidewalls ofthe patterned ribbons.

FIG. 66 provides a schematic diagram for boron doping processing. Afterthe KOH refining step, boron doping for formation of top p+ contact isconducted.

FIG. 67 provides a schematic diagram for phosphorous doping processing

FIG. 68 provides a schematic diagram showing sidewall passivationprocessing.

FIG. 69 provides a schematic diagram showing processing for theformation of a KOH etching window.

FIG. 70 provides micrographs showing KOH etching processing and bottomboron doping processing.

FIG. 71 provides images showing transfer of the solar cell ribbons fromthe source wafer using a PDMS transfer device.

FIG. 72 provides a schematic diagram illustrating contact printing andplanarization processing steps.

FIG. 73 provides an imaging showing the results of metallizationprocessing.

FIG. 74 provides a schematic diagram of the metallization processshowing an Al metal layer, SiO₂ dielectric layer, Cr/Au layer, solarcell, planarizing layer and device substrate.

FIGS. 75A and 75B provide schematic diagrams exemplifying theexpressions “lateral dimensions” and “cross sectional dimensions” asused in the present description. FIG. 75A provides a top plan view ofprintable semiconductor elements comprising 4 semiconductor ribbons6005. In the context of this description the expression “lateraldimension” is exemplified by the length 6000 and width 6010 of thesemiconductor ribbons 6005. FIG. 75B provides a cross sectional view ofthe printable semiconductor elements comprising 4 semiconductor ribbons6005.

FIG. 76 shows an array of printable GaAs/InGaAlP red LEDs printed on PETsubstrates.

DETAILED DESCRIPTION OF THE INVENTION

Referring to the drawings, like numerals indicate like elements and thesame number appearing in more than one drawing refers to the sameelement. In addition, hereinafter, the following definitions apply:

“Collecting” and “Concentrating”, as applied to optics and opticalcomponents, refers to the characteristic of optical components anddevice components that they direct light from a relatively large areaand direct that light to another area, in some cases a smaller area. Inthe context of some embodiments, collecting and concentration opticalcomponents and/or optical components are useful for light detection orpower harvesting by printed inorganic solar cells or photodiodes.

“Printable” relates to materials, structures, device components and/orintegrated functional devices that are capable of transfer, assembly,patterning, organizing and/or integrating onto or into substrateswithout exposure of the substrate to high temperatures (i.e. attemperatures less than or equal to about 400 degrees Celsius). In oneembodiment of the present invention, printable materials, elements,device components and devices are capable of transfer, assembly,patterning, organizing and/or integrating onto or into substrates viasolution printing or contact printing.

“Printable semiconductor elements” of the present invention comprisesemiconductor structures that are able to be assembled and/or integratedonto substrate surfaces, for example using by dry transfer contactprinting and/or solution printing methods. In one embodiment, printablesemiconductor elements of the present invention are unitary singlecrystalline, polycrystalline or microcrystalline inorganic semiconductorstructures. In one embodiment, printable semiconductor elements areconnected to a substrate, such as a mother wafer, via one or more bridgeelements. In this context of this description, a unitary structure is amonolithic element having features that are mechanically connected.Semiconductor elements of the present invention may be undoped or doped,may have a selected spatial distribution of dopants and may be dopedwith a plurality of different dopant materials, including P and N typedopants. Printable semiconductor elements and structures of the presentinvention may include holes or perforations through one dimension of theelements to facilitate their release from a wafer by the introduction ofa chemical release agent. The present invention includes microstructuredprintable semiconductor elements having at least one cross sectionaldimension (e.g., thickness) selected over the range of 1 micron to 1000microns. The present invention includes nanostructured printablesemiconductor elements having at least one cross sectional dimension(e.g., thickness) selected over the range of 1 to 1000 nanometers. In anembodiment, a printable semiconductor element of the present inventionhas a thickness dimensions less than of equal or 1000 microns,preferably for some applications a thickness dimensions less than orequal to 100 microns, preferably for some applications a thicknessdimensions less than or equal to 10 microns and preferably for someapplications a thickness dimensions less than or equal to 1 microns.

Printable semiconductor elements useful in many applications compriseselements derived from “top down” processing of high purity bulkmaterials, such as high purity crystalline semiconductor wafersgenerated using conventional high temperature processing techniques. Insome methods and systems of the present invention, printablesemiconductor elements of the present invention comprise compositeheterogeneous structures having a semiconductor operational connected toor otherwise integrated with at least one additional device component orstructure, such as a conducting layer, dielectric layer, electrode,additional semiconductor structure or any combination of these. In somemethods and systems of the present invention, the printablesemiconductor element(s) comprises a semiconductor structure integratedwith at least one additional structure selected from the groupconsisting of: another semiconductor structure; a dielectric structure;conductive structure, and an optical structure (e.g., optical coatings,reflectors, windows, optical filter, collecting, diffusing orconcentration optic etc.). In some methods and systems of the presentinvention the printable semiconductor element(s) comprises asemiconductor structure integrated with at least one electronic devicecomponent selected from the group consisting of: an electrode, adielectric layer, an optical coating, a metal contact pad asemiconductor channel. In some methods and systems of the presentinvention, printable semiconductor elements of the present inventioncomprise stretchable semiconductor elements, bendable semiconductorelements and/or heterogeneous semiconductor elements (e.g.,semiconductor structures integrated with one or more additionalmaterials such as dielectrics, other semiconductors, conductors,ceramics etc.). Printable semiconductor elements include, printablesemiconductor devices and components thereof, including but not limitedto printable LEDs, lasers, solar cells, p-n junctions, photovoltaics,photodiodes, diodes, transistors, integrated circuits, and sensors.

“Cross sectional dimension” refers to the dimensions of a cross sectionof device, device component or material. Cross sectional dimensionsinclude the thickness, radius, or diameter of a printable semiconductorelement. For example, printable semiconductor elements having a ribbonshape are characterized by a thickness cross sectional dimension. Forexample, printable semiconductor elements having a cylindrical shape arecharacterized by a diameter (alternatively radius) cross sectionaldimension.

“Longitudinally oriented in a substantially parallel configuration”refers to an orientation such that the longitudinal axes of a populationof elements, such as printable semiconductor elements, are orientedsubstantially parallel to a selected alignment axis. In the context ofthis definition, substantially parallel to a selected axis refers to anorientation within 10 degrees of an absolutely parallel orientation,more preferably within 5 degrees of an absolutely parallel orientation.

The terms “flexible” and “bendable” are used synonymously in the presentdescription and refer to the ability of a material, structure, device ordevice component to be deformed into a curved shape without undergoing atransformation that introduces significant strain, such as straincharacterizing the failure point of a material, structure, device ordevice component. In an exemplary embodiment, a flexible material,structure, device or device component may be deformed into a curvedshape without introducing strain larger than or equal to 5%, preferablyfor some applications larger than or equal to 1%, and more preferablyfor some applications larger than or equal to 0.5%.

“Semiconductor” refers to any material that is a material that is aninsulator at a very low temperature, but which has a appreciableelectrical conductivity at a temperatures of about 300 Kelvin. In thepresent description, use of the term semiconductor is intended to beconsistent with use of this term in the art of microelectronics andelectrical devices. Semiconductors useful in the present invention maycomprise element semiconductors, such as silicon, germanium and diamond,and compound semiconductors, such as group IV compound semiconductorssuch as SiC and SiGe, group III-V semiconductors such as AlSb, AlAs,Aln, AlP, BN, GaSb, GaAs, GaN, GaP, InSb, InAs, InN, and InP, groupIII-V ternary semiconductors alloys such as Al_(x)Ga_(1-x)As, groupII-VI semiconductors such as CsSe, CdS, CdTe, ZnO, ZnSe, ZnS, and ZnTe,group I-VII semiconductors CuCI, group IV-VI semiconductors such as PbS,PbTe and SnS, layer semiconductors such as PbI₂, MoS₂ and GaSe, oxidesemiconductors such as CuO and Cu₂O. The term semiconductor includesintrinsic semiconductors and extrinsic semiconductors that are dopedwith one or more selected materials, including semiconductor havingp-type doping materials and n-type doping materials, to providebeneficial electrical properties useful for a given application ordevice. The term semiconductor includes composite materials comprising amixture of semiconductors and/or dopants. Specific semiconductormaterials useful for in some applications of the present inventioninclude, but are not limited to, Si, Ge, SiC, AlP, AlAs, AlSb, GaN, GaP,GaAs, GaSb, InP, InAs, GaSb, InP, InAs, InSb, ZnO, ZnSe, ZnTe, CdS,CdSe, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, PbS, PbSe, PbTe, AlGaAs, AlInAs,AlInP, GaAsP, GaInAs, GaInP, AlGaAsSb, AlGaInP, and GaInAsP. Poroussilicon semiconductor materials are useful for applications of thepresent invention in the field of sensors and light emitting materials,such as light emitting diodes (LEDs) and solid state lasers. Impuritiesof semiconductor materials are atoms, elements, ions and/or moleculesother than the semiconductor material(s) themselves or any dopantsprovided to the semiconductor material. Impurities are undesirablematerials present in semiconductor materials which may negatively impactthe electrical properties of semiconductor materials, and include butare not limited to oxygen, carbon, and metals including heavy metals.Heavy metal impurities include, but are not limited to, the group ofelements between copper and lead on the periodic table, calicum, sodium,and all ions, compounds and/or complexes thereof.

“Plastic” refers to any synthetic or naturally occurring material orcombination of materials that can be molded or shaped, generally whenheated, and hardened into a desired shape. Exemplary plastics useful inthe devices and methods of the present invention include, but are notlimited to, polymers, resins and cellulose derivatives. In the presentdescription, the term plastic is intended to include composite plasticmaterials comprising one or more plastics with one or more additives,such as structural enhancers, fillers, fibers, plasticizers, stabilizersor additives which may provide desired chemical or physical properties.

“Elastomer” refers to a polymeric material which can be stretched ordeformed and return to its original shape without substantial permanentdeformation. Elastomers commonly undergo substantially elasticdeformations. Exemplary elastomers useful in the present invention maycomprise, polymers, copolymers, composite materials or mixtures ofpolymers and copolymers. Elastomeric layer refers to a layer comprisingat least one elastomer. Elastomeric layers may also include dopants andother non-elastomeric materials. Elastomers useful in the presentinvention may include, but are not limited to, thermoplastic elastomers,styrenic materials, olefenic materials, polyolefin, polyurethanethermoplastic elastomers, polyamides, synthetic rubbers, PDMS,polybutadiene, polyisobutylene, poly(styrene-butadiene-styrene),polyurethanes, polychloroprene and silicones. Elastomers provideelastomeric stamps useful in the present methods.

“Transfer device” refers to a device or device component capable ofreceiving, relocating, assembling and/or integrating an element or arrayof elements, such as one or more printable semiconductor elements.Transfer devices useful in the present invention include conformabletransfer devices, having one or more contact surfaces capable ofestablishing conformal contact with elements undergoing transfer. Thepresent methods and compositions are particularly well suited forimplementation in connection with a transfer device comprising anelastomeric transfer device. Useful elastomeric transfer devicesincluding an, elastomeric stamp, composite elastomeric stamp, anelastomeric layer, plurality of elastomeric layers and an elastomericlayer coupled to a substrate such as a glass, ceramic, metal or polymersubstrate.

“Large area” refers to an area, such as the area of a receiving surfaceof a substrate used for device fabrication, greater than or equal to 36square inches.

“Conformal contact” refers to contact established between surfaces,coated surfaces, and/or surfaces having materials deposited thereonwhich may be useful for transferring, assembling, organizing andintegrating structures (such as printable semiconductor elements) on asubstrate surface. In one aspect, conformal contact involves amacroscopic adaptation of one or more contact surfaces of a conformabletransfer device to the overall shape of a substrate surface or thesurface of an object such as a printable semiconductor element. Inanother aspect, conformal contact involves a microscopic adaptation ofone or more contact surfaces of a conformable transfer device to asubstrate surface leading to an intimate contact with out voids. Theterm conformal contact is intended to be consistent with use of thisterm in the art of soft lithography. Conformal contact may beestablished between one or more bare contact surfaces of a conformabletransfer device and a substrate surface. Alternatively, conformalcontact may be established between one or more coated contact surfaces,for example contact surfaces having a transfer material, printablesemiconductor element, device component, and/or device depositedthereon, of a conformable transfer device and a substrate surface.Alternatively, conformal contact may be established between one or morebare or coated contact surfaces of a conformable transfer device and asubstrate surface coated with a material such as a transfer material,solid photoresist layer, prepolymer layer, liquid, thin film or fluid.

“Placement accuracy” refers to the ability of a transfer method ordevice to transfer a printable element, such as a printablesemiconductor element, to a selected position, either relative to theposition of other device components, such as electrodes, or relative toa selected region of a receiving surface. “Good placement” accuracyrefers to methods and devices capable of transferring a printableelement to a selected position relative to another device or devicecomponent or relative to a selected region of a receiving surface withspatial deviations from the absolutely correct position less than orequal to 50 microns, more preferably less than or equal to 20 micronsfor some applications and even more preferably less than or equal to 5microns for some applications. The present invention provides devicescomprising at least one printable element transferred with goodplacement accuracy.

“Optical communication” refers to a configuration of two or moreelements wherein one or more beams of electromagnetic radiation arecapable of propagating from one element to the other element. Elementsin optical communication may be in direct optical communication orindirect optical communication. “Direct optical communication” refers toa configuration of two or more elements wherein one or more beams ofelectromagnetic radiation propagate directly from a first device elementto another without use of optical components for steering and/orcombining the beams. “Indirect optical communication” on the other handrefers to a configuration of two or more elements wherein one or morebeams of electromagnetic radiation propagate between two elements viaone or more device components including, but not limited to, waveguides, fiber optic elements, reflectors, filters, prisms, lenses,gratings and any combination of these device components.

The present invention relates to the following fields: collectingoptics, diffusing optics, displays, pick and place assembly, verticalcavity surface-emitting lasers (VCSELS) and arrays thereof, LEDs andarrays thereof, transparent electronics, photovoltaic arrays, solarcells and arrays thereof, flexible electronics, micromanipulation,plastic electronics, displays, transfer printing, LEDs, transparentelectronics, stretchable electronics, and flexible electronics.

The present invention provides optical devices and device arrays, forexample LED arrays, laser arrays, optical sensors and sensor arrays, andphotovoltaic arrays, comprising printable, high quality inorganicsemiconductor elements assembled and integrated via transfer printingtechniques. Assembly and integration methods of the present inventioninclude dry contact printing of printable semiconductor elements,replica molding for making device substrate such as device substrateshaving integrated optical components (e.g., lens arrays) and laminationprocessing steps.

In an embodiment, the invention provides a new type of display thatgenerates images by the coordinated operation of assemblies oflight-emitting diodes (LEDs) or other light emitting or collectingdevices. The images may be high definition, as those on a computermonitor or television, or they may provide simple illumination in a waysimilar to fluorescent lights. The invention is formed by the assemblyof small inorganic light emitting devices, transistors, and electricallyconductive interconnects. Transfer printing and other novel fabricationprocesses may be used to perform the assembly of these components and toimpart new functionality to them, e.g. stretchability.

The invention may be built on a range of substrates, including rigidmaterials (e.g. glass), flexible materials (e.g. thin plastic), and evenstretchable materials (e.g. elastomers), imparting a number of benefitsto these display and illumination products, including a high-degree oftransparency, flexibility, and/or stretchability, as well as mechanicaltoughness and low weight. The invention is therefore useful for a numberof applications, including architectural elements and devices that candynamically conform to complex contours of objects, for example in theaerospace, transportation, medical, and fashion industries. The lightemitters (LEDs) used are capable of high-speed operation and greatbrightness, enabling effective display of images even in full sunlight(e.g. for outdoor displays).

The novel transfer printing and other fabrication processes of thepresent invention, in addition to imparting functionality to thedisplays, enable the production of systems of the invention at costslower than those required to produce other, less versatile types ofdisplays (e.g. conventional LED displays). The novel transfer printingand other fabrication procedures also enables systems of the inventionto achieve levels of brightness, large-area coverage, transparency,mechanical properties, operating lifetime, and/or resolutioncombinations that are not available to other display technologies(liquid crystal displays, organic LED displays, conventional LEDdisplays, cathode ray tube displays, etc.).

FIG. 1 provides a schematic showing optical systems provided by thepresent invention. As shown in FIG. 1, the present invention provides anumber of classes of optical systems and related methods of making thesesystems, including systems for light generation and systems for lightharvesting, comprising printed inorganic optical and optoelectronicsystems with integrated optical components in registry. Light generationsystems include printed LED displays, micro LED devices, passive matrixLED displays, active matrix LED displays, printed VCSEL systems andprinted semiconductor laser arrays, optionally comprising lightdiffusing optics, light focusing optics and/or light filtering optics.Light harvesting systems include sensors, such as artificial eyesensors, sphere/plane convertible stamp sensors and sphere confirmablestretchable semiconductor based sensors, and photovoltaic systems, suchas photovoltaic arrays, microsolar cells, optionally comprisingcollecting optics. Optical systems of the present invention includestretchable devices and systems, flexible devices and systems and rigiddevices and systems.

FIG. 2 A-E provides schematic diagrams of optical systems of the presentinvention comprising printable semiconductor elements. FIG. 2A shows aprinted LED array with integrated optical diffuser. FIG. 2B shows aVCSEL array on a silicon chip with integrated optical fibers. FIG. 2Cshows a printed photovoltaic array with integrated optical collectors.FIG. 2D shows an artificial eye sensor comprising a printed photodiodearray on a collecting lens. FIG. 2E shows a sheet scanner having bothlight sensing and light generation functionality and comprising aprinted array LED and photodiode components and integrated collectionoptics provided on a polymer or other low cost substrate.

FIG. 3 provides a process flow schematic for the fabrication of a singlepixel element of a printed inorganic active matrix LED display of thepresent invention. Panel 1 illustrates the step of preparing gateelectrodes on substrate. Panel 2 illustrates the step of spin-coatthin-film adhesive on the patterned substrate. Panel 3 illustrates thestep of printing a thin-film transistor structure on the adhesive layer,for example using contact printing. Panel 4 illustrates the step ofdepositing (or printing) electrode lines so as to interconnect theprinted transistor structure. Panel 5 illustrates the step of printingan LED structure onto one or more electrodes. In some embodiments,bonding of these elements is achieved by cold-welding. Panel 6illustrates the step of encapsulating or planarizing the devicecomponents, for example using a photocurable epoxy. Panel 7 illustratesthe step of depositing or printing electrical contacts to top the LEDelectrode structure.

FIG. 4 provides a schematic illustration (not to scale) of a printedactive matrix LED display on a glass substrate. The display showncomprises 100 pixels and is an approximately 11 inch display. Thin filmtransistor (TFT) elements, LED elements, gate lines, anode lines anddata lines of the device are indicated in FIG. 4. TFT and LED structuresare assembled via printing, for example using one or more elastomericstamps. Metal lines are patterned with shadow masks. The bottom plateholds LED structures, data and gate lines, and TFT structures. The topplate holds the anode lines.

FIG. 5 provides photographs (FIG. 5A) and operating current-voltagecharacteristics (FIG. 5B) of a single pixel of an active matrix LEDdisplay on a (transparent) glass substrate. As shown in FIG. 5A thesingle pixel of an active matrix LED display comprises a printed TFTstructure, a LED structure, gate electrode and electrical interconnects.FIG. 5B provides a plot of current (A) verses drive bias (V) for thesingle pixel of an active matrix LED display.

FIG. 6 provides photographs of a 64 pixel active matrix LED display on a(transparent) glass substrate. FIG. 6A provides a photograph of a 64pixel partial LED display (Note: missing top contacts) comprising 1 mmtransistors printed on to the device substrate and ILEDs manually placedon the substrate. In the device shown in FIG. 6A, pixels are provided ata 4 mm pitch. FIG. 6B provides a photograph of a printed silicon TFTwith interdigitated channel (thin green line) for high-currentoperation. FIG. 6C provides a photograph of two pixels illuminated byplacing a transparent common anode electrical contact against the LEDs.

FIG. 7A provides a process flow schematic for the fabrication of asingle pixel element of a printed inorganic passive matrix LED display.Panel 1 illustrates the step of spin coating a layer of elastomerprecursor onto a receiving surface of the substrate. After spin castingthe elastomer precursor layer is at least partially cured. Panel 2illustrates the step of depositing an electrode. Panel 3 illustrates thestep of printing an ILED structure onto the electrode, for example viacontact printing. Panel 4 illustrates the step of laminating the topelectrode, wherein the top electrode is housed on a second substrate.This processing steps achieves contacting of the printed LED structure.

FIG. 7B provides a process flow schematic for establishing electricalcontact by compression of a (soft) substrate/layer. Panel 1 illustratesthe step of placing a component between 2 substrates (at least onesoft—e.g., elastomer) prepatterned with integrated electrodes. Panel 2illustrates the step of activating the substrate surfaces for strongbonding upon contact, for example via oxygen plasma treatment forbonding PDMS to PDMS or PDMS to glass. Panel 3 illustrates the step ofpressing the two substrates together, for example by “sandwiching” thecomponent. In this processing step sufficient pressure is applied todeform the soft layer and bring the two surfaces into contact. Afterbonding, the electrical contact is maintained by residual pressure.Panel 4 illustrates a similar process as shown in Panel 3, usingoptional relief features to facilitate contact and engineer a strongerbonding interface, for example via reduction of stress concentrationpoints.

FIG. 8 provides a schematic illustration (not to scale) of a printedpassive matrix printed inorganic LED display. As shown in FIG. 8, thedisplay comprises a bottom substrate, electrode network, printed ILED,PDMS layer and top substrate.

FIG. 9 provides photographs of passively addressed printed inorganic LEDdisplays/arrays on glass and flexible PET substrates.

FIG. 10 provides a process flow schematic for printing inorganic lightemitters and collectors via cold-weld bonding techniques. Panel 1illustrates the step of evaporating metal (e.g. gold, indium, silver,etc.) onto an inorganic element disposed on a transfer device (e.g., anelastomeric stamp). As shown in panel 1 metal is also evaporated on thereceiving surface of a substrate. Panel 2 illustrates the step ofcontacting the stamp and inorganic element to receiving surface, andoptionally applying heat or pressure to induce cold-welding of metalfilms. Panel 3 illustrates the step of removing the stamp, therebyresulting in transfer and assembly of the inorganic elements via contactprinting.

FIG. 11 provides a process flow schematic for printing techniques of thepresent invention using a donor cartridge and cold-weld bondingtechnique. In this method a cartridge is patterned with SU-8. ILEDstructures are placed on the patterned surface of the cartridge. A stampis used to take up the ILED structures and subsequently print the ILEDstructures on a substrate prepatterned with electrodes via transferprinting. The bottom panel of FIG. 11 shows an example of a LEDstructure printed and assembled using this method.

FIG. 12 provides a schematic of an optical system of the presentinvention wherein diffusing optics are integrated with printable LEDstructures. In this embodiment, PDMS is molded on rough polystyrene. Acomparison of panels (a) and (b) show the affect of incorporation of adiffuser in this optical system. The diffuser can be a rough molded PDMSstructure. This figure demonstrates that diffusers can effectivelyincrease the size of the luminous region.

FIG. 13 provides a schematic of diffusing optics comprising a pluralityof radial density gradient scattering centers useful for LED lightingsystems of the present invention. As shown in this figure a printed LEDstructure under metal is provided in optical communication with aplurality of optical scattering centers. The bottom panel in FIG. 13shows a cross sectional view of scattering centers comprising relieffeatures in a transparent substrate.

FIG. 14A provides an exemplary epilayer structure for the fabrication ofprintable micro-LEDs. As shown in this figure, the epilayer structurecomprises a series of device layers, sacrificial layers and a handlewafer. Individual layers in the epilayer structure are shown in thebottom panel of FIG. 14A. FIG. 14B provides an exemplary epilayerstructure for the fabrication of printable micro-LEDs comprising quantumwell emissive layers. The epilayer structure comprises a series ofsemiconductor layers provided between p-cladding and n-cladding layers.Specific compositions of each layer in the epilayer structure areprovided. FIG. 14C provides a table indicating the composition,thickness, doping and functionality of each layer in the epilayerstructure for the fabrication of printable micro-LEDs.

FIG. 14D illustrates an example of a mother wafer from which printablep-on-n GaAs solar cells may be produced by photolithography and etchinglayers 9 through 4 and selectively removing layer 3 by a wet chemicaletch.

FIG. 14E illustrates provides another example of a mother wafer fromwhich printable n-on-p GaAs solar cells may be produced byphotolithography and etching layers 9 through 4 and selectively removinglayer 3 by a wet chemical etch.

FIG. 15 provides schematic diagrams illustrating the imperceptiblepixilation/high degree of transparency from low fill-factor, micro-sized(<˜100 micron footprint) LEDs. As shown in the top panel of this figure,the optical system comprises: (i) a first glass coated ITO or a low-fillfactor metal mesh layer; (ii) printed micro LEDS structures; and (iii) asecond glass coated ITO or a low-fill factor metal mesh layer. Top viewsare provided corresponding to the off state and the on state. Amagnification of the top view is also provided showing the positioningof micro LED structures.

FIG. 16 provides schemes for the release of printable light-emittinginorganic semiconductor micro-elements: micro-LEDs or VCSELs. Scheme 1describes the release of such elements by encapsulating them in apolymer, e.g. photoresist, and releasing them from the wafer on whichthey were grown by selectively etching an Al_(x)Ga_(1-x)As (x>about 70%)sacrificial layer using hydrofluoric acid. Scheme 2 describes release byencapsulating them in a conformal dielectric (e.g. silicon nitride) andreleasing them from the wafer by selectively oxidizing the AlGaAs andetching the oxidized material using aqueous potassium hydroxide. Scheme3 describes release by encapsulating them with a polymer, e.g.photoresist, followed by selective etching of a buried GaAs sacrificiallayer using an aqueous mixture of citric acid and hydrogen peroxide. InScheme 3, the AlGaAs protects the underside of the light emittingelement from the citric acid-based etchant.

FIG. 17A provides a schematic process flow diagram illustratingfabrication of integrated solar cell/collector arrays by printing solarcells. As shown in this figure solar microcells are fabricated in adense array on a wafer. A stamp is brought into contact with the densesolar cell array and used to transfer the solar cells from the wafer toa target assembly substrate. As shown in FIG. 17A, the solar microcellsin the array are transferred onto the back electrode of the targetassembly substrate via contact printing. FIG. 17B provides a schematicprocess flow diagram illustrating fabrication of integrated solarcell/collector arrays via interconnection of registry of an opticalarray. As shown in this figure solar microcells are printed on a targetsubstrate. The substrate is further processed to provide front electrodeand an insulating layer. Next, a molded micro array of microlenses isintegrated into the optical system such that each lens in the array isindividually addressed to at least one solar microcell. FIG. 17Cprovides a schematic process flow diagram illustrating the operation ofthe integrated solar cell/collector arrays. In this embodiment, eachmicrolens collector/concentrator is individually addressed and opticallyaligned with a single crystal solar cell, as shown in the top panel ofFIG. 17C. Also shown in this figure are the front electrode, insulatinglayer and back electrode. The bottom panel of FIG. 17C schematicallyshows interaction of sun light with the optical system.

FIG. 18A provides a schematic diagram (not to scale) showing operationof the integrated collecting/concentrating optics (lens) and solar-cellarrays of an optical system of the present invention. The collection andfocusing of incident light is provided by the ray diagrams provided inthis figure, which show light incident to the optical concentrator isfocused on the active area of a printed microsolar cell addressed to theoptical concentrator. A gold layer provides a bonding layer to affix themicrosolar cell to the device substrate. FIG. 18B shows an expanded viewof a microsolar cell of the present invention assembled via printing.The solar cell is a multilayer structure comprising an antireflectionlayer, top contact, p-n junction and a bottom aluminum layer.

FIG. 19 provides a schematic diagram illustrating design and fabricationstrategies of the present invention for light harvesting via reductionof semiconductor materials costs in a sheet-like form factor. Thecollector size is approximately 2 mm, the solar cell size isapproximately 0.1 mm, and the area multiplication (ratio of collectorarea and solar cell area) is approximately 400. As demonstrated by thecalculation show in this figure 1 ft² of processed semiconductor waferresults in approximately 400 ft² of light-harvesting area. Thiscalculation demonstrates that the methods and optical systems of thepresent invention provide a high efficiency and low cost fabricationstrategy for high performance photovoltaic devices and systems.

FIG. 20 provides a schematic diagram of a collecting/concentrating opticand heterogenously composed solar cell of a solar cell array(sympevolent/diventegration) of the present invention. As shown in thisfigure, collecting optics are provided in optical communication with anitride/phosophide and/or arsenide solar cell and silicon solar cellassembled on the device substrate via contact printing. FIG. 20 alsoprovides ray diagram of the incident light showing collection and focusfunctionality of a concentrator and individually addressed solar cells.Single crystal multilayer solar cells (i.e. third generation solarcells) are typically grown by MOCVD and are constrained by the necessityof crystal lattice mismatch between layers. In our system differentabsorbing layers can have arbitrary lattices and the materials selectedfor optimal spectrum absorption for each layer.

FIG. 21 provides a schematic process flow diagram for fabrication of anintegrated solar cell and lens array using a combination of replicamolding methods and contact printing. As shown in this figure a masterlens array is used to generate a negative replica mold, for example viareplica molding or imprinting techniques. Next, the molded PDMS layer isused to generate a plano-concave polymer lens array by casting thepolymer against the negative replica. As shown in FIG. 21, solar cellsprinted onto a device substrate are provided in optical communicationwith the lens array so as to generate an optical system of the presentinvention.

FIG. 22 demonstrates the ability of Fresnel lenses, a type ofconcentrating/collecting optic, to focus light to a small area for usein light harvesting systems described by the present invention. Fresnellens arrays can be used as optical concentrators due to theiradvantageous features such as thin form factor and light weight comparedwith conventional lenses. FIG. 22 shows a focal area measurement forspherical and cylindrical Fresnel lenses.

FIG. 23 provides a schematic diagram illustrating an optical system ofthe present invention wherein horizontal light pipes and/or waveguidesare provided for light harvesting. This optical system uses transparent,structured media of appropriate index of refraction to capture normally-or obliguely-incident light and guide it in the plane of the substrateto a solar cell or solar cell array. As shown in this figure a pluralityof waveguide structures, such as light pipes, are in opticalcommunication and individually addressed a solar cell such that thelight collected by each waveguide is directed to the solar cell.

FIG. 24 provides a schematic showing an exemplary printable siliconsolar cell fabricated using a silicon on insulator SOI wafer. The solarcell comprises a doped top surface with a P/As mixture and is supportedby a buried oxide layer of the 501 wafer. FIG. 24 shows the solar cellmultilayer structure comprising a n⁺-Si (P/As) layer and p-Si(B) layer.In an embodiment, the silicon solar cell is assembled into aphotovoltaic system via a method comprising the steps of: (i) patterningthe surface of the SOI wafer, for example using ICP-RIE, so as to definethe physical dimensions of one or more printable solar cell structures;(ii) releasing printable solar cell structures, for example via HFundercut etch processing wherein the buried oxide layer is selectivelyetched thereby releasing the printable solar cell structures; (iii)retrieving the silicon printable structures, for example using anelastomeric (e.g., PDMS) stamp which is contacted with the releasedprintable solar cell structures and pulled away from the SOI substrate,thereby transferring the printable solar cell structures from thesubstrate to the elastomeric stamp; (iv) depositing back metallizationof the printable solar cell structures, for example using CVD, PVD orthermal deposition methods; (v) transferring printable siliconstructures having back metallization from the elastomeric stamp to ametallized device substrate via contact printing, optionally incombination with a cold-welding bond step; (vi) annealing the solar cellstructures printed onto the device substrate to activate Al-doped p+region; (vii) casting an insulating/planarization layer on the printedsolar cell structures; (viii) depositing top electrical contacts ontothe printed solar cells, for example using a combination ofphotolithography and evaporation processing; (iv) depositing a Si₃N₄antireflecting coating on the solar cell array and (v) integrating theconcentrator optics, such as a lens array, to the top of the micro-solarcell array.

FIG. 25 provides a schematic process flow diagram illustrating a methodof transferring a printable solar cell to substrate using contactprinting and subsequent cold welding processing to affix the solar cellto a device substrate. As shown in the figure, the solar cell iscontacted with an elastomeric stamp (e.g. PDMS stamp). A thin gold layeris provided to the external aluminum layer of the printable solar cell.The surface of the solar cell having the thin gold layer is contactedwith a metallized receiving surface of the device substrate. Theelastomeric stamp is subsequently moved away from the substrateresulting in transfer of the printable solar cell to the devicesubstrate. Finally the transferred solar cell is annealed to activatethe aluminum doped p⁺ region.

FIG. 26 provides a schematic diagram (not to scale) showing a top view(in parallel) of an exemplary configuration for top contacts to solararrays of the present invention. Microsolar cells (shown in gray) havingwidths of approximately 100 microns and lengths of approximately 1millimeter are provided in an array format on a device substrate. Metalfeatures are provided having widths of about 60 microns and lengths onthe order of 1 inch. The metal features provide the top contacts of asolar cell device array of the present invention.

FIG. 27 provides a schematic diagram of an “artificial eye” sensor ofthe current invention. The sensor comprises an inorganic photodiodearray distributed on a lens having spherical curvature. Various lensshapes and angles are shown in FIG. 27. FIG. 28 provides a schematicdiagram illustrating the process of wrapping a planar sheet around aspherical surface demonstrating the necessity of stretchability in anexemplary “artificial eye” sensor. As shown in FIG. 28, conformalpositioning of the planar sheet on a spherical receiving surfacerequires some degree of stretchability to avoid failure.

Example 1 Ultra Thin Flexible Solar (UTFS) Devices and Methods

Photovoltaic (PV) energy conversion is the direct conversion of sunlightinto electricity using a semiconductor device structure. The most commontechnology in the PV industry is based on single crystalline andpolycrystalline silicon technology. Presently, silicon PV technology hashigh materials costs, due to the relatively inefficient use of the bulksilicon material. In conventional methods, bulk crystalline silicon issawn into wafers, which are then processed into solar cells and solderedtogether to form the final module. Typical multicrystalline efficienciesare on the order of 15%; high-performance, single-crystal silicon hasbeen produced with 20% efficiency. For this type of solar cell, 57% ofthe cost is in materials, and of that total material cost 42% comes fromthe crystalline Si. In addition, these modules are rigid and heavy.

There is currently interest in thin-film PV technologies, since thesesystems have the potential for lower cost (due to less active materialusage), and also have the ability to be deposited onto polymersubstrates for low weight and flexibility. Presently, investigation isongoing in thin film materials such as amorphous silicon, cadmiumtelluride (CdTe) and copper indium gallium diselenide (CIGS). CIGS-basedPV cells have demonstrated cell efficiencies of 19.2%, the highest ofany polycrystalline thin film material. These cells are small,laboratory-scale devices; to date, the highest large-area flexiblemodule efficiencies are on the order of 10%. Cheaper thin filmsemiconductors enable material cost savings, but induce higherprocessing costs as the cells need to be fabricated/processed on largearea substrates. Also, only low/moderate temperature processes can beused on the final assembly substrate

Ideally, one would like to combine the single crystalline technologies,which have a high efficiency and large industrial knowledge base, withthe low-cost, lightweight and flexible nature of the thin-filmtechnologies. The present Ultra Thin Flexible Solar (UTFS) technologyprovides the means of achieving a lightweight, flexible solar modulewith both high efficiency and lower materials costs. Since we start witha pure silicon substrate, it enables the use of high precision andhigh-temperature wafer processing to fabricate state-of-the-artperformance solar cells.

The present invention provides Ultra Thin Flexible Solar (UTFS) Devicesgenerated via a novel fabrication platform combining:

-   -   1. An ultra-thin (less than 20 microns thickness) crystalline        silicon solar cell, grown and etched on a single-crystal silicon        wafer. The size of this cell is much less (e.g., two orders of        magnitude) than those used in previous silicon-transfer        processes, for example the solar cells have lengths and width        that are on the order of 100 microns in some embodiments;    -   2. An innovative microstamping process which removes the silicon        solar cell from the mother wafer and transfers it to a flexible        polymer substrate; and    -   3. Automated interconnect of the transferred cells to form the        final module, if required.

Methods and systems of the present invention utilize a microstampingcontact printing process that avoids certain problems associated withpast silicon transfer technologies; namely, the cracking and defectsformed by attempting to transfer relatively large pieces of silicon. Thepresent microstamping contact printing process also reduces the overallmodule assembly cost (compared to conventional die pick-and-placetechniques) as thousands of micro-cells can be transfer-printed inparallel.

The solar cell devices and fabrication methods of the present inventionhave several advantages including its applicable to a wide variety ofhigh quality crystalline semiconductors including but not limited tosingle crystalline silicon and other higher-efficiency materials, suchas Gallium Arsenide (GaAs). In addition, combination of an ultra-thinsolar cell and a polymer substrate provides devices and systems havinglow weight and good mechanical flexibility. Polypropylene is a polymeruseful for this aspect of the present systems and methods.

FIG. 29 provides a schematic of a process flow diagram showing a methodfor making a microsolar cell array of the present invention. As shown inFIG. 29, a Si wafer is processed so as to generate a plurality ofsilicon-based microsolar cell ribbons. The silicon-based microsolar cellribbons are released from the substrate. The released ribbons are liftedoff and transferred to a polymer device substrate via contact printingusing an elastomeric transfer device. Ribbons of silicon are assembledinto a photovoltaic device array via subsequent processing including thestep of providing device interconnects to the microsolar cells, andoptionally light collection and concentrating optics such as a lensarray.

As shown in FIG. 29, thin (˜10 μm) silicon solar cells are transferredto polymer substrates and interconnected to form a module in a mannerthat retains flexibility. Selection of the thickness of the siliconcomponent of the silicon solar cell is an important parameter in thepresent invention. In an embodiment, for example, the thin siliconcomponent is thick enough to achieve a desired efficiency of ˜15%. Theprimary impact of thickness on the cell performance is on the collectedcurrent; with a thinner cell, less photons are absorbed and hence lesscurrent is generated. FIG. 30, provides a plot of Si Layer thicknessverses short circuit current (J_(SC)) as calculated for a simulated Sicell exposed to the AM1.5 standard spectrum used for terrestrial-basedsolar cells. For these calculations, we assume that the light makesthree total passes through the Si layer (Once initially, once afterreflection off of the back, and again after subsequent reflection off ofthe front side), and that the quantum efficiency of the cell isrelatively high (90%).

From the results of the calculation, a silicon thickness on the order of10-15 microns would be required in some embodiments of the presentinvention to achieve the desired AM1.5 efficiency of 15%. It should benoted that this relatively thick absorber layer is due to the fact thatsilicon is an indirect-bandgap material. A similar solar cell using adirect-bandgap material, such as gallium arsenide, can be thinner.

Multilayer stacks of printable silicon ribbons can be formed by using acombination of RIE and wet etching. FIG. 31 provides scanning electronmicrographs showing sequential formation of Si multilayer ribbon stacksuseful in some embodiments of the present invention. These arehigh-quality, dimensionally-uniform ribbons. By appropriate processinginto p-n diodes, these can be converted into silicon solar cells.

Previous silicon transfer techniques typically glue the liftoff layer toa glass carrier, and also transfer relatively large areas of silicon (˜5cm²). One of the major issues with these transfer techniques are cracksand defects formed in the Si layer.

By transferring smaller pieces of Si, we avoid cracking the transferredSi layer. We also use an innovative ‘stamping’ process using apoly-dimethylsiloxane (PDMS) material to grip and transfer the siliconto a polymer substrate.

A polymer such PET or PEN is useful for the substrate in terrestrialapplications. For space-based applications, a space-rated polyamide suchas Kapton can be used as a substrate material. Kapton is mechanicallysuitable for space applications, although it is known to degrade in lowearth orbit due to the presence of atomic oxygen (AO).

After transfer of the Si ribbons to the polymer substrate, they areelectrically interconnected to form the final solar cell. In someembodiments, individual Si ribbons are connected in a series connection.FIG. 32 provides a schematic diagram of a connection scheme where the Siribbons comprise p-type silicon with a thin n-type layer on top to formthe emitter. After transfer, connection lines comprising conducting inkare printed onto the ribbons, either via a direct-write process or viascreen-printing. The bottom panel shows the as-transferred Si Ribbonsand the top panel shows the connection (direct-write orscreen-printing). Only four Si Ribbons are shown for clarity.

One of the attractions of the present technology is that it isapplicable to other absorber materials; for example, the samemicrostamping process has been used to transfer gallium arsenide. Theuse of these materials has been demonstrated in concentrator solarmodules. FIG. 33 provides a schematic of a solar cell array of thepresent invention using a PDMS concentrator array for concentratingsolar illumination.

Bulk crystalline silicon is selling for over $50 per kilogram.Presently, silicon plants are coming online to meet the needs of boththe PV and microelectronic industries. It is anticipated that even ifbulk Si costs fall back to pre-2001 values of $20/kg, as capacitycatches up with demand, overall costs will remain high. As mentionedpreviously, present-day Si PV is formed by sawing a crystalline ingotinto wafers, then processing the wafers into cells, and then solderingthe cells together to form the final module. The present industry trendis towards thinner cells, since Si thicknesses beyond ˜50 microns (seeFIG. 30) do not absorb any more light. Currently, the thinnest Si PVcells are on the order of 250 microns thick (about ¼ mm). Handling suchthin wafers in the ‘normal’ PV cell processing and integration is achallenge.

Conventional wire-sawing techniques result in approximately 60% waste;that is, 60% of the original silicon ingot winds up as dust. For a 20%efficient module formed out of 250-micron-thick wafers, the siliconmaterials costs are estimated at $0.40/Watt. Considering that theultimate goal of the PV industry is to achieve $1/Watt, the materialscosts for such a module are significant.

For the present UTFS technology, the semiconductor materials costs ismuch lower. Even assuming a waste of 50%, with a 15% module with15-micron thick silicon the materials costs are estimated at˜$0.02/Watt. This cost savings is primarily due to the betterutilization of the silicon; in effect, we are ‘spreading’ the siliconover a greater area than in convention methods and devices.

The printing process involves the liftoff of the device element from themother substrate onto the stamp, followed by the delivery of theseelements from the surface of the stamp to the target substrate. Byappropriate design of the undercut etch and liftoff of these elementsfrom their mother substrate, it is possible to perform the liftoff stepwith high yields. The transfer is accomplished either by stronger vander Waals bonding between the element and the target substrate thanbetween the element and the stamp or by the use of strong adhesivelayers on the target substrate. In both cases, the area of contactbetween the element and the coated or uncoated surface of the targetsubstrate must be sufficiently high to enable efficient transfer. Inmost case, the dominant requirement is for the bottom surfaces of theelements and the top surfaces of the target substrate to be sufficientlysmooth to enable large contact areas. This requirement can be satisfiedfor a wide range of systems of interest. The systems considered in thisexample are extremely well situated to meet these flatness requirements,since they involve elements with polished back surface and targetsubstrates that will consist of polished semiconductor wafers.

FIG. 34 provides images showing results of printing single crystalsilicon onto plastic, glass, Si wafers, InP wafers and thin film a-Si.The microstamping process of the present invention is compatible with awide range of substrates.

In an embodiment, the stamps used to pick-up and transfer the ‘chiplets’are typically made by casting and curing a ˜1 cm thick piece of rubberagainst a “master” substrate. The patterns present on the surface of the“master” can be replicated with extremely high fidelity (down to thenanometer scale) when low modulus silicone such as poly-dimethylsiloxane(PDMS) are used to fabricate the stamps. However, single layer stampsmade out of this soft material can easily be deformed during theprinting process. As a result, coarse placement accuracy is sometimesrealized with these soft stamps. The present invention includes,however, use of composite stamps that provide excellent placementaccuracy and pattern fidelity. U.S. patent application Ser. No.11/115,954, for “Composite Patterning Devices for Soft Lithography”,issued as U.S. Pat. No. 7,195,733, describes composite stamps designsand methods useful in the present invention and is hereby incorporatedby reference in its entirety.

A low modulus material, such as PDMS, is used for the first layer toallow conformal (i.e. with no air void) contact with the top surface ofthe semiconductor device components. Additional thin layers (such asplastic films or glass fibers) having a high in-plane modulus is used toprevent in-plane mechanical deformations during the transfer. By usingsuch composite stamp designs, in-plane distortions (as observed under ahigh magnification microscope) lower than 5 microns over a ˜16×16 cm²area are achievable in soft lithography printing techniques.

In an embodiment, the printing systems comprise: (1) stamps with designsoptimized for efficient transfer and for minimal distortions in theplacement of the printed elements, (2) physical mounting jigs for thesestamps and translation stages for moving the substrate and the stampwith sub-micron precision, (3) load cells interfaced to the stamps forforce feedback control of contact during the ‘inking’ and ‘printing’steps, and (4) vision systems that allow multilevel registration. Insome embodiments, printing systems useful in the present invention canhandle target device substrates with sizes up to 300×400 mm and donorwafers with diameters up to 4 inches. The registration is accomplishedwith a long working distance microscope and CCD camera that allowsalignment marks on the surfaces of transparent stamps to be registeredto alignment marks on the donor wafers and the target substrates. Theaccuracy with which the stamps can be positioned and aligned is ˜0.5 μm.The registration accuracy, when implemented with new types ofdistortion-free composite stamps, is also in this range.

Example 2 Conformable Thin Film LED Lighting Systems

The present invention provides printing based techniques that provide ameans to integrate inorganic light emitting diodes with thin flexiblesubstrates. This approach, as implemented with automated high precisionprinter systems, is useful for fabricating light-weight and mechanicallyconformable interior lighting elements for automotive and otherapplications, in a manner that is compatible with low costmanufacturing.

The present methods and systems involve fabrication of conformableILED-based thin film lighting devices followed by application tosurfaces using adhesive bonding. Methods may also optionally includeprocessing involving incorporation of encapsulation and planarizingmaterials, coatings and layers to enhance mechanical properties of thesystem. The sizes of the thin film structures, the numbers and spacingsof the ILEDs and other aspects determine the device designs for specificapplication.

Transfer printing of micro/nanoscale semiconductor devices from sourcewafers to wide ranging classes of target substrates, including thinplastic sheets, is used in the present invention to fabricateconformable LED lighting systems. FIG. 35 shows a schematic illustrationof an exemplary process of the present invention, as applied to theprinting of printable inorganic semiconductor-based LEDs. The transferof the ink to, and from, an elastomeric stamp is affected by kineticallymodulating the adhesion energy at the stamp-‘ink’ and ‘ink’-substratesurfaces. In the case of FIG. 35, printable inorganicsemiconductor-based LEDs play the role of the ‘ink’. This type ofprocess is capable of manipulating semiconductor materials or deviceswith lateral dimensions between 100 nm and hundreds of microns, and withthicknesses between 20 nm and hundreds of microns. Electronic andoptoelectronic systems of various types have been demonstrated with thisapproach, on substrates ranging from rigid glass, polymer andsemiconductor wafers to thin flexible sheets of plastic. The printingitself is performed with a fully automated printer that provides bothforce and feedback control of the transfer process, together withmicroscope based vision systems for alignment. FIG. 36 provides an imageand a schematic illustration of a printer useful in the present methodsof fabricating conformable ILED-based thin film lighting systems.

Using such an approach, a small passive matrix 8×8 lighting pad has beenassembled with blue inorganic LEDs assembled on a polycarbonatesubstrate with prepatterned metallic interconnects. FIG. 37 providesimages of square (part a) and linear (part b) lighting devices thatcomprise passively addressed blue inorganic LEDs assembled on plasticsubstrates via contact printing. The device in part (b) represents ademonstration of a thin film lighting device comprising a conformableILED-based lighting system of the present invention. A small version ofa blue ILED-based thin film lighting device is also shown in FIG. 37.

In some embodiments, conformable LED lighting systems of the presentinvention have utility for lighting applications for automobiles andother vehicles. In some embodiments, for example, the present inventionprovides reliable and low cost ILED-based thin film lighting devicesthat can be integrated in a conformal way with the relevant surfaces ofan automobile or other vehicle.

FIG. 39 provides a schematic process flow diagram of a method offabricating a conformable LED lighting system of the present invention.As shown in FIG. 39, an adhesive material is (NOA) is used to fix ILEDand top/bottom substrate before injection of PDMS. In some embodiments,external power lines are installed before injection of PDMS to preventcontamination of the external pad region, as shown in FIG. 39. In someembodiments, sample is installed with tilted angle in a vacuum chamberto remove air in injected PDMS, as shown in FIG. 39. In someembodiments, pressure is applied between two substrates to keep acontact between the ILEDs and electrodes, as shown in FIG. 39. Injectionof a PDMS encapsulating layer is useful for improving the bendingcharacteristics of the device (particularly in slow bending motion) andinjection of PDMS achieves a stable contact property.

FIG. 39 provides a process flow diagram for fabricating a ILED lightdevice of the present invention comprising a flexible strip. As shown inthis figure, a thin PDMS layer is provided on a PET film. Electrodes aredefined and deposited via evaporation of Ti/Au and shadow maskingtechnique. Printable ILED device elements are transferred and assembledonto the substrate via contact printing. As shown in FIG. 39, anadhesive (e.g., NOA) is provided to the bottom substrate, and the topsubstrate is bonded to the device. The external pad and wire is fixedand a PDMS adhesive is inject and cured, optionally under vacuumconditions, so as to encapsulate/planarize the ILED structures.

FIG. 40 provides a cross sectional view of a conformal ILED lightingsystem of the present invention comprising top and bottom PET substrates(approximately 175 microns thick), ILEDS structures (approximately 100microns thick), electrodes and a PDMS encapsulating coating or layer(approximately 20-40 microns thick).

FIG. 41 provides images of ILED lighting systems of the presentinvention in an unbent state, a first bent state with a bending radiusof 7 cm, a second bent state with a bending radius of 5 cm, third bentstate with a bending radius of 4.5 cm, a fourth bent state with abending radius of 3 cm and in a state upon release of the bendingstress. The images in FIG. 41 confirm that conformal ILED lightingsystems of the present invention provide useful optical properties inbent configurations.

FIG. 42 provides an image of a flexible strip light made of blue LEDsand thin kapton substrates with bending radius equal to 0.85 cm.

TABLE 1 Summary of Experimental Conditions for Testing the MechanicalProperties of Conformal ILED Sensors. Bending Substrate OperatingOperating Radius Operating # PDMS PET Electrode Electroplating Check 1Injection Check 2 (Max.) Check 3 Note 1 ◯ ◯ Ti/Au(5/300 nm) X 50% ◯ 50%3 cm 50% Improve 2 ◯ ◯ Ti/Au(5/300 nm) X 90% ◯ 90% 3 cm 80% 3 ◯ ◯Ti/Au(5/300 nm) X 70% ◯ 70% 3 cm 70% 4 ◯ ◯ Al/Ti/Au(700/5/50 nm) X 50% —— — — 5 X ◯ Al/Ti/Au(500/5/100 nm) ◯ 80% ◯ 80% 3 cm 80% Improve 6 X ◯Ti/Au(5/300 nm) X 60% ◯ 60% 3 cm 50% However, working problem afterrepeatable test 7 ◯ ◯ Ti/Au(5/300 nm) ◯ X X X X X Delamination ofelectrode from substrate for electroplating

In results of experiment, we observe that operation of the presentconformable ILED-based lighting systems is improved in cases of thickerelectrode and PDMS coatings or encapsulating layers on PET. However, itis difficult to fabricate a strip-light with only thicker electrodebecause alignment of ILED on electrode (by hand) is difficult. In someembodiments, the process uses a by using an aligner to provide morestable and accurate assembly. An optimized system for some embodimentscombines thicker electrode, PDMS coating on PET and removing tweezingprocess by hand.

FIG. 43 provides schematics showing two methods for assembling ILEDstructures on the device substrate. The lower panel shows an assemblymethod using alignment by hand and the upper panel show an assemblymethod using an aligner. When we use an aligner to align ILED onelectrode, the number of operating ILED are greatly increased because adamage of electrodes is reduced compared to use tweezers. This methodalso enhances alignment between the ILED and electrode structures.

Example 3 Printing-Based Assembly of Solar Cells and Solar Cell Arrays

FIG. 44 provides a schematic for the formation of a micro single crystalsilicon solar cell with low-level concentrating lens. In the first step(a) the micro structures are transferred from PDMS onto an embeddedelectrode which serves as the back electrical contact for the device.The silicon is transferred by laminating the PDMS onto the electrodesurface and slowly peeling the PDMS back. Next, in step (b),planarization followed by the formation of the top metal contacts isperformed. The device is completed by integrating a low concentrationcylindrical lens array made from PDMS onto the device (step c). In thisfinal step it can be seen that the device was designed such that therows of silicon cells align with the focal point of the lens array.

FIG. 45 provides images of a silicon solar cell transferred to a glasssubstrate. (a) Optical image of a single cell on a glass substrate withboth top and bottom electrical contacts. (b) Typical I-V response for adevice shown in (a) under AM 1.5.

FIG. 46 provides images of a solar cell array joined to cylindricalcollecting optics. (a) Picture of the final fully integrated device withcylindrical lens array. (b) Picture of the same device without theincorporation of the lens array.

FIG. 47 provides a schematic diagram for generating optical concentratorarrays with integrated metal contacts onto mS-Silicon solar cells. Theprocess starts off with retrieval of a metal mesh pattern from asubstrate (shown dark blue) via a PDMS molded lens array. In someembodiments, the lens array/mesh pattern is laminated in registry ontoan array of silicon solar cells.

FIG. 48 describes the process flow for generating solar cells andintegrated concentrating optics.

FIG. 49 provides images of a micro solar cell array printed onto goldbus lines on glass substrates via a thin PDMS adhesive layer.

FIG. 50 provides a schematic illustration of microcells of (a)vertical-type, (b) transverse-type, (c) combination of both types. Theprocessing scheme for producing bulk quantities of single crystal Simicro-ribbons from bulk silicon wafers has been recently developed. Theapproach begins with a controlled deep reactive ion etching process tocreate well-defined ribbon structures. Subsequent side-wall passivationeither from angled electron beam evaporation deposition of metals orfrom chemical vapor deposition of SiO₂/Si₃N₄ can function as a physicalmask for highly anisotropic wet chemical (e.g. KOH) etching. Thissingle-step etching process thus can produce micro-ribbon arrays inprinting-ready forms. Both vertical and transverse type pn-junctions areprovided by the present invention, which has its own advantages over theother in microcell configurations. Vertical type pn-junctions have beenmainly pursued for photovoltaic applications due to its easy processingwith bulk wafers and large junction area. On the other hand, transversetype pn-junctions have more choices in terms of transfer methods, usablesubstrates, and a possibility of back-side illumination (i.e.eliminating shadowing issues due to metal grids), while they may exhibitlimited performance on account of their intrinsically small junctionarea. Another design of the present invention is a combination ofvertical and transverse junctions, which may take above-mentionedadvantages. All of the junction structures (n⁺-p-p⁺) can be readilyfabricated by selective doping process, in which thermal diffusion ofspin-on-dopant is conducted with PECVD-grown SiO₂ doping mask ofappropriate thickness and pattern. For vertical type cells, n⁺-emitterdoping is done first before creating microcell patterns, while backp⁺-doping as back-surface-field (BSF) is accomplished after themicrocell patterning process, by a transfer of the patterned microcellsonto a substrate covered with dopants and a subsequent thermaldiffusion. After this BSF doping step, the microcells can be transferredagain to any desired substrate. For transverse type cells, process ofselective n⁺ and p⁺ doping is more straightforward than vertical cells,simply by using patterned doping masks repetitively. Microcells arecreated after finishing these doping processes. For the combination typecells, front side doping is obtained in a similar manner with transversetype cells, while back side doping is implemented by following theprocedure of BSF formation in vertical type cells.

The present invention also includes ILED displays with matrix structureas well as strip-light without a method using PDMS cassette.

Example 4 Electrical Interconnection Strategies for Printed OpticalSystems

The present invention provides methods and systems useful forestablishing good electrical connection of semiconductor-based opticalsystems fabricated by contact printing methods. Processing steps anddevice geometries of the present invention provide efficient,mechanically robust and highly conductive electrical connection betweenelectronic devices and/or device components assembled via contactprinting. The present processing steps and device geometries arecompatible with a range of electrical interconnect patterning andprocessing techniques including photolithographic processing, depositiontechniques and/or soft lithographic (e.g., contact printing) patterning.

a. Planarizing Fabrication Strategies and Device Geometries

In an aspect, the present invention provides planarizing processingsteps and planar device geometries that minimizes, or completely avoids,degradation of electronic performance of device electrical interconnectsarising from step edges of semiconductor elements, such as semiconductorelectronic devices and device components, assembled on a devicesubstrate via contact printing. In the context of this description,“planarizing” refers to a process wherein one or more printablesemiconductor elements are integrated with a device substrate such thata surface structure is formed having an exposed surface with asubstantially planar geometry. Preferably for some applications, theexposed surface having a substantially planar geometry includes one ormore individual surfaces of the printed semiconductor element(s) thatcan be patterned with device electrical interconnect structures, forexample using optical lithography and deposition techniques. A planargeometry generally refers to a surface configuration wherein all pointson the surface occupy a common plane. In the context of thisdescription, however, a substantially planar geometry includes somedeviation from an absolutely planar configuration. In some embodiments,for example, a substantially planar geometry includes deviations insurface position from an absolutely planar configuration of less than 2microns, preferably for some embodiments deviations in surface positionfrom an absolutely planar configuration of less than 1 micron, and morepreferably for some embodiments deviations in surface position from anabsolutely planar configuration of less than 500 nanometers.

Planarization in the present invention is achieved by providingmaterials, layers and/or structures adjacent to printed semiconductorelements such that the step edges of these structures are reduced and/orminimized, thereby allowing for effective patterning and integration ofelectrical interconnection structures. In an embodiment, for example,the space between adjacent printed semiconductor elements is filled withor otherwise occupying by portions of device substrate itself, othermaterials, layers or structures provided to the device substrate or acombination of these. Planarizing may be achieved in the presentinvention using a number of processing methods including embedding oneor more printable semiconductor elements into a receiving surface of adevice substrate or a planarizing layer provided thereon. Alternatively,planarizing in the present invention may be achieved in the presentinvention may be achieved by assembling printable semiconductor elementson a receiving surface of a device substrate by contact printing andsubsequently providing materials or layers adjacent to the printablesemiconductor elements, and in some embodiments between adjacent printedsemiconductor elements, so reduce or minimize the step edges of theprinted structures.

In an embodiment of this aspect, the present invention provides a methodof making a semiconductor-based optical system comprising the steps of:(i) providing a device substrate having a receiving surface; (ii)assembling one or more printable semiconductor elements on the receivingsurface of the substrate via contact printing; and (iii) planarizing theprintable semiconductor element(s) assembled on the receiving surface,thereby making the semiconductor-based optical system. In an embodiment,the planarizing step generates a substantially planar and/or smooth topsurface on the device substrate including the printable semiconductorelement(s). In methods useful for device fabrication applications, thesubstantially planar and/or smooth top surface generates includesexposed surfaces of one or more planarized printable semiconductorelements assembled on the receiving surface. Methods and systems havinga planar and/or smooth top surface included exposed surfaces of one ormore planarized printable semiconductor elements is beneficial forproviding electrical contact to the planarized printable semiconductorelements via additional processing steps, such as lithographicpatterning of electrodes/device interconnect structures. In a method ofthe present invention, the printable semiconductor element comprises aunitary inorganic semiconductor structure. In a method of the presentinvention, the printable semiconductor element comprises a singlecrystalline semiconductor material.

Optionally, a method of the present invention further comprises the stepof curing, polymerizing or cross linking the planarizing layer havingthe printable semiconductor element embedded therein, thereby fixing theprintable semiconductor element in the planarizing layer. Planarizinglayers of the methods and systems of this aspect of the presentinvention are also useful for mechanical integrating printablesemiconductor elements with a device substrate. Optionally, a method ofthe present invention further comprising the steps of patterning one ormore electrodes/electrical interconnects to one or more exposed surfacesof the planarized printable semiconductor element included in thesubstantially planar and/or smooth top surface. Patterning electrodesand interconnects can be achieved by means known in the art including,but not limited to, optical lithography, deposition techniques (e.g.,CVD, PVD, thermal deposition, sputtering deposition, plasma depositionetc.), soft lithography (e.g., contact printing) and combinations ofthese. Optionally, a method of the present invention comprising thesteps: (i) assembling a plurality of printable semiconductor elements onthe receiving surface of the substrate via contact printing; and (ii)planarizing the plurality of printable semiconductor elements assembledon the receiving surface.

In an embodiment, the planarizing step generates a substantially planartop surface on the device substrate having the printable semiconductorelement(s). Preferably for some application the substantially planar topsurface comprises an exposed surface of each of the printedsemiconductor elements assembled on the receiving surface. Preferablyfor some embodiments of this aspect, the planarized semiconductorelements assembled on the receiving surface exhibit step edge featuresthat are less than 2 microns, preferably for some applications less than1 micron and more preferably for some applications less than 500nanometers. This aspect of the invention is useful for generatingstructure that can be effective electrically interconnected, for exampleusing lithographic patterning and thin film deposition methods.

In an embodiment, the planarizing step of this method comprisesembedding the printable semiconductor element(s) into the devicesubstrate. Techniques for embedding one or more printable semiconductorelements directly into a device substrate include raising thetemperature of a polymer device substrate so as to achieve a physicalstate (e.g. viscosity) capable of displacement during contact printing.Alternatively, planarizing may be achieved by direct integration ofprintable semiconductor elements into prepatterned recessed features inthe receiving surface of the receiving substrate.

In another embodiment, the planarizing step of this method comprisesembedding the printable semiconductor element(s) in a planarizing layerprovided on the receiving surface of the device substrate. In thecontext of this description, a planarizing layer refers to a layer ofmaterial supported by the receiving substrate such that printedsemiconductor elements can be embedded or implanted into the planarizinglayer. In some embodiments, planarizing layers comprise materials, suchas low viscosity fluids, that are capable of physical displacement orrearrangement so as to accommodate printed semiconductor elements.Optionally, planarizing layers of the present inventon are capable ofchemical or physical transformation after receiving printablesemiconductor elements to harden, solidify or otherwise change phase orviscosity such that the embedded printed semiconductor elements are heldin place. Optionally, the planarizing layer is a prepolymer layer thatis polymerized after receiving the printable semiconductor elements.Optionally, the planarizing layer is a polymer layer that is crosslinked after receiving the printable semiconductor elements.

The present invention includes methods wherein the planarizing layer isprovided to the receiving surface or structure thereon and subsequentlycontacted with the printable semiconductor element(s). In thisembodiment, the planarizing layer receives the printable semiconductorelements assembled on the receiving surface. Alternatively, the presentinvention includes methods wherein the planarizing layer is provided tothe receiving surface after the step of assembling the printablesemiconductor element(s) on the receiving surface. In this embodiment,the planarizing layer is provided so as to fill-in or build up regionsof the receiving substrate so as to planarize the printed semiconductorelements.

Planarizing layers of the present invention may comprise a range ofmaterials including, but not limited to, polymers, prepolymers,composite materials having a polymer component, gels, adhesives andcombinations thereof. For some applications, planarizing layerspreferably comprise one or more low viscosity materials capable ofphysical displacement or rearrangement to accommodate and embedprintable semiconductor elements. In an embodiment, for example, aplanarizing layer comprises a material having a viscosity selected overthe range of 1-1000 centipoise. Planarizing layers for some devicefabrication applications have a thickness comparable to the printablesemiconductor elements assembled on a receiving surface. In anembodiment, a planarizing layer of the present invention has a thicknessselected over the range of 10 nanometers to 10000 microns. In someembodiments, a planarizing layer of the present invention has athickness similar (e.g., within a factor of 1.5) to that of theprintable semiconductor elements assembled on the receiving surface. Inan embodiment the thickness of the planarizing layer is selected overthe range of 0.0003 mm to 0.3 mm, preferably for some applicationsselected over the range of 0.002 mm to 0.02 mm

The present invention also includes optical systems comprisingplanarized printable semiconductor elements. In an embodiment, asemiconductor-based optical system of the present invention comprises:(i) a device substrate having a receiving surface; and (i) one moreplanarized printable semiconductor elements supported by the receivingsurface; wherein the device substrate having the one or more printablesemiconductor elements has the substantially planar top surface thatincludes at least a portion of the printable semiconductor elements,wherein the printable semiconductor elements comprise a unitaryinorganic semiconductor structure having a length selected from therange of 0.0001 millimeters to 1000 millimeters, a width selected fromthe range of 0.0001 millimeters to 1000 millimeters and a thicknessselected from the range of 0.00001 millimeters to 3 millimeters. In anembodiment, the printable semiconductor element comprises asemiconductor structure having a length selected from the range of 0.02millimeters to 30 millimeters, and a width selected from the range of0.02 millimeters to 30 millimeters, preferably for some applications alength selected from the range of 0.1 millimeters to 1 millimeter, and awidth selected from the range of 0.1 millimeters to 1 millimeter,preferably for some applications a length selected from the range of 1millimeters to 10 millimeters, and a width selected from the range of 1millimeter to 10 millimeters. In an embodiment, the printablesemiconductor element comprises a semiconductor structure having athickness selected from the range of 0.0003 millimeters to 0.3millimeters, preferably for some applications a thickness selected fromthe range of 0.002 millimeters to 0.02 millimeters. In an embodiment,the printable semiconductor element comprises a semiconductor structurehaving a length selected from the range of 100 nanometers to 1000microns, a width selected from the range of 100 nanometers to 1000microns and a thickness selected from the range of 10 nanometers to 1000microns.

Optionally, the system of the present invention further comprises aplanarizing layer provided on the receiving surface of the devicesubstrate, wherein the printable semiconductor elements are embedded inthe planarizing layer. In a system of the present invention, theprintable semiconductor elements are printable electronic devices orelectronic device components, such as LEDs, solar cells, lasers,sensors, transistors, diodes, p-n junctions, integrated circuits,photovoltaic systems or a component of these.

FIGS. 54A and 54B provides schematic diagrams of systems of the presentinvention comprising planarized printable semiconductor elements.Printable semiconductor elements 5010 are embedded in the devicesubstrate 5000 itself (See FIG. 54A) or alternatively in a planarizinglayer 5020 (See FIG. 54B) provided on a receiving surface of devicesubstrate 5000. As shown in these FIGS. 54A and 54B the planarizedconfiguration results in a top exposed surface 5015 having asubstantially planar geometry which includes some deviation from anabsolute planar configuration. As shown in these figures, top exposedsurface 5015 including exposed surfaces of the planarized printablesemiconductor elements 5010 in addition to exposed surfaces of substrate5000 or planarizing layer 5020. FIG. 55 provides a flow diagramillustrating processing steps in methods of the present invention formaking semiconductor-based optical systems comprising planarizedprintable semiconductor elements, such as printable semiconductor-basedelectronic devices and device components.

A benefit of using planarized device configurations and planarizationmethods of the present invention is that it allows good electricalcontact with planarized printable semiconductor elements to beestablished in further processing steps, such as lithographic anddeposition processing. FIG. 56 provides experimental resultscharacterizing the impact of step edges on establishing electricalcontact to and/or between printable semiconductor elements. Experimentalresult corresponding to printed semiconductor elements comprisingsilicon bars having step edge dimensions of 290 nm, 700 nm, 1.25 micronsand 2.5 microns. Inset of FIG. 56 shows a micrograph and schematicshowing the device and electrical contact geometries. As shown in thisfigure, good conductivity (e.g., resistance less than 10 ohm) isobserved for step edge dimensions up to 1.25 microns. For step edgedimensions equal to 2.5 microns, however, a significant decrease inconductivity (e.g., resistance equal to 1.7 ohm) is observed.Planarizing methods of the present invention, therefore, havesignificant value in minimizing the magnitude of step edges in assembledprintable semiconductor elements, thereby accessing planarized devicegeometries capable of effective implementation of device interconnectsand electrodes.

In a system of this aspect, the printable semiconductor element(s)comprises a semiconductor structure having a length selected from therange of 0.02 millimeters to 30 millimeters, and a width selected fromthe range of 0.02 millimeters to 30 millimeters. In a system of thisaspect, the printable semiconductor element(s) comprises a semiconductorstructure having at least one longitudinal physical dimension selectedfrom the range of 0.1 millimeters to 1 millimeter. In a system of thisaspect, the printable semiconductor element(s) comprises a semiconductorstructure having at least one longitudinal physical dimension selectedfrom the range of 1 millimeters to 10 millimeters. In a system of thisaspect, the printable semiconductor element(s) comprises a semiconductorstructure having at least one cross sectional dimension selected fromthe range of 0.0003 millimeters to 0.3 millimeters. In a system of thisaspect, the printable semiconductor element(s) comprises a semiconductorstructure at least one cross sectional dimension selected from the rangeof 0.002 millimeters to 0.02 millimeters.

The system relates, in an aspect, to a plurality of planarized printablesemiconductor elements supported by said receiving surface; wherein saiddevice substrate having said printable semiconductor element has saidsubstantially planar top surface that includes at least a portion ofsaid planarized printable semiconductor elements, wherein each of saidprintable semiconductor element comprises a semiconductor structurehaving a length selected from the range of 0.0001 millimeters to 1000millimeters, a width selected from the range of 0.0001 millimeters to1000 millimeters and a thickness selected from the range of 0.00001millimeters to 3 millimeters.

In an embodiment of this aspect, the system further comprises aplanarizing layer provided on said receiving surface of said devicesubstrate, wherein said printable semiconductor element is embedded insaid planarizing layer. In an embodiment of this aspect, system furthercomprises one or more electrodes or electrical interconnects patternedon said substantially planar top surface. In an embodiment of thisaspect, said printable semiconductor element is a printable electronicdevice or electronic device component. In an embodiment of this aspect,the printable semiconductor element is a LED, a solar cell, a laser, asensor, diode, p-n junction, transistor, integrated circuit or acomponent thereof. In an embodiment of this aspect, the printablesemiconductor element comprises said semiconductor structure integratedwith at least one additional structure selected from the groupconsisting of: another semiconductor structure; a dielectric structure;conductive structure, and an optical structure. In an embodiment of thisaspect, the printable semiconductor element comprises said semiconductorstructure integrated with at least one electronic device componentselected from the group consisting of: an electrode, a dielectric layer,an optical coating, a metal contact pad and a semiconductor channel. Inan embodiment of this aspect, the printable semiconductor element has athickness selected from the range of 100 nanometers to 100 microns.

The present invention includes other strategies for avoid or mitigatingthe effect of step edges in establishing electrical connection betweento and/or between printable semiconductor elements. In some embodiments,for example, the printable semiconductor elements are fabricate suchthat they have at least one side having a sloping or otherwise graduallytapering edge. The sloping edge provides a gradual change at the edge ofthe printable semiconductor element, as opposed to an right angleconfiguration where the change on the edge of the printablesemiconductor element is abrupt. In these embodiments, printablesemiconductor elements are assembled such that a side having the slopingedge(s) is exposed upon contact with the receiving surface. Thisgeometry allows access to, and subsequent processing on, the exposedside having the sloping edges for integration of electricalinterconnects. The present of the sloping edges of the printablesemiconductor elements, therefore, reduces the impact of step edges inintegrating electrical interconnection structures and electrodes.

b. Electrical Interconnection Using Mesh and Grid Electrodes

The present invention also include device geometries and processingmethods wherein an electrically conducting mesh or grid electrode isused to electrically interconnect printable semiconductor elementsassembled via contact printing. Mesh and grid electricalinternconnection elements and/or electrodes are optionally assembled viacontact printing methods on a receiving surface of a device substrate,optical systems or optical component or assembled via contact printingmethods on exposed surfaces of printed semiconductor elements,optionally using a conformable transfer device. Advantages of the use ofmesh and grid electrodes include that fact that they can be effectivelypatterned over large areas, thereby, allowing for greater tolerance inthe placement accuracy of printable semiconductor elements assembled viacontact printing due. This processing and design advantage results in arelaxation of processing constraints and device geometry tolerancesinvolved in contact printing-based assembly of printable semiconductorelements. For example, use of mesh and grid electrodes and deviceinterconnects significantly relaxes design and placement constraints onthe alignment and positions of the printable semiconductor elementsassembled by contact printing. In addition, use of mesh and gridelectrodes allows a large number of printable semiconductor elements tobe effectively electrically interconnected in a single (or small number)of processing steps. Further, the thickness and/or fill factor of meshor grid electrodes can be selected such that they are opticallytransparent, which allows these components to be implemented in opticalsystems requiring transmission of electromagnetic radiation through themesh or grid, such as displays, photovoltaic systems, optical sensingsystems and multifunctional optical systems. In some embodiments, thegrid or mesh is more than 50% optical transparent at a selectedwavelength of electromagnetic radiation.

In an embodiment, methods of the present invention comprise the step ofproviding an electrically conducting grid or mesh in electrical contactwith at least a portion of the printable semiconductor elementsassembled on a receiving surface of a device substrate, therebyestablishing electrical contact from the mesh to at least a portion ofthe printable semiconductor elements. In an embodiment, the electricalconnection from the grid or mesh to said printable semiconductorelements is established by contact printing. The grid or mesh providesone or more electrodes or electrical interconnection structures in someof the optical systems of the present invention. The step of providingthe grid or mesh in electrical contact with at least a portion of theprintable semiconductor elements may be carried out via contactprinting-based processing, for example using a conformable transferdevice such as an elastomeric (e.g., PDMS) stamp. In some embodiments,for example, this processing step comprises the step of transferring thegrid or mesh onto the receiving surface of device substrate via contactprinting, and subsequently assembling printable semiconductor elementson one or more surfaces of the printed grid or mesh, therebyestablishing electrical connection between these device elements.Alternatively, in another method this processing step comprises the stepof transferring via contact printing the grid or mesh onto one or moreexposed surfaces of printable semiconductor elements previouslyassembled onto the receiving surface of the device substrate, therebyestablishing electrical connection between these device elements.

In another embodiment, the present invention provides a method of makinga semiconductor-based optical system comprising the steps of: (i)providing an optical component having an internal surface; (ii)providing a electrically conducting grid or mesh on said internalsurface of said optical component; (iii) providing a device substratehaving a receiving surface; (iv) assembling a plurality of printablesemiconductor elements on said receiving surface of said substrate viacontact printing; wherein each of said printable semiconductor elementscomprise a semiconductor structure having a length selected from therange of 0.0001 millimeters to 1000 millimeters, a width selected fromthe range of 0.0001 millimeters to 1000 millimeters and a thicknessselected from the range of 0.00001 millimeters to 3 millimeters; and (v)transferring said optical component having said grid or mesh to saiddevice substrate, wherein said optical component is positioned on top ofsaid semiconductor elements assembled on said on said receiving surfaceof said substrate, wherein said electrically conducting grid or mesh isprovided between said optical component and said semiconductor elements,and wherein said metal grid or mesh is provided in electrical contactwith at least a portion of said printable semiconductor elements. In anembodiment, the printable semiconductor element comprises asemiconductor structure having a length selected from the range of 0.02millimeters to 30 millimeters, and a width selected from the range of0.02 millimeters to 30 millimeters, preferably for some applications alength selected from the range of 0.1 millimeters to 1 millimeter, and awidth selected from the range of 0.1 millimeters to 1 millimeter,preferably for some applications a length selected from the range of 1millimeters to 10 millimeters, and a width selected from the range of 1millimeter to 10 millimeters. In an embodiment, the printablesemiconductor element comprises a semiconductor structure having athickness selected from the range of 0.0003 millimeters to 0.3millimeters, preferably for some applications a thickness selected fromthe range of 0.002 millimeters to 0.02 millimeters. In an embodiment,the printable semiconductor element comprises a semiconductor structurehaving a length selected from the range of 100 nanometers to 1000microns, a width selected from the range of 100 nanometers to 1000microns and a thickness selected from the range of 10 nanometers to 1000microns.

Optionally steps (i) and/or (v) in the method recited above is carriedout via contact printing methods, for example using a conformabletransfer device such as an elastomeric stamp. In an embodiment, theelectrically conducting mesh or grid comprises one or more metals. In anembodiment, the electrically conducting mesh or grid comprises one ormore semiconductor materials. In a method of the present invention, theprintable semiconductor element comprises a unitary inorganicsemiconductor structure. In a method of the present invention, theprintable semiconductor element comprises a single crystallinesemiconductor material.

In some methods, said step of transferring said optical component on topof said semiconductor elements assembled on said on said receivingsurface of said substrate comprises printing said optical component ontop of said semiconductor elements assembled on said on said receivingsurface of said substrate using contact printing. For example, methodsof the present invention include the step of assembling the printablesemiconductor element said receiving surface via dry transfer contactprinting, optionally using a conformable transfer device such as anelastomeric transfer device.

Mesh or grids useful as electrical interconnect structures and/orelectrodes may comprise any conductive material including metals andsemiconductors (including doped semiconductors). In some embodiments,mesh or grids useful as electrical interconnect structures and/orelectrodes may have a thickness selected over the range of 10 nanometersto 10000 microns. Use of thin and/or low fill factor grid or meshstructures is useful for some embodiments, as these structures can beimplemented such that they are optically transparent, for exampletransmitting greater than 10%, 30% 50% or 70% of incidentelectromagnetic radiation having a selected wavelength. Fill factors ofmesh or grid structures for some applications range between 5% and 80%,preferably between 10-50%. In some embodiments, use of mesh or gridstructures having a fill factor less than 30% is preferred.

Mesh or grid structures useful for electrical interconnect structuresand/or electrodes of the present invention may optionally be alaminated, planarized and/or encapsulated structure. In an embodiment,for example, the mesh or grid structure is bonded to an elastomericlayer, such as a PDMS layer, to facilitate handling, transfer and/orintegration, for example using contact printing methods, optionallyusing a conformable transfer device such as an elastomeric stamp. Usefulelastomeric layers for some applications have thicknesses ranging from 1micron to 1000 microns. Use of an elastomeric layer in some embodimentsallows the grid or mesh electrode or interconnect structure to deformand move so as to generate good electrical connect with printedsemiconductor elements. In some embodiments, the mesh or grid structureis also coupled to a support, such as glass or polymer substrate. In anembodiment, for example, the mesh or grid structure is mechanicallycoupled to an elastomeric layer coupled to and a glass or polymersubstrate. In some configurations, the elastomer layer is positionedbetween the mesh or grid structure and the glass or polymer substrate.Use of a support, such as a glass or polymer substrate, facilitatesintegration of grid or mesh electrode or interconnect structures intooptical systems of the present invention.

Use of grid and mesh electrode and/or electrical interconnectionstructures is beneficial for establishing electrical connection of arange of printable semiconductor elements. Optionally, the printablesemiconductor element in these methods is an electronic device orcomponent of an electronic device, such as an LED, a laser, a solarcell, a sensor, a diode, a transistor, and a photodiode. Optionally, theprintable semiconductor element in these methods has a thicknessselected from the range of 100 nanometers to 100 microns

In an embodiment, the present invention provides a semiconductor-basedoptical system comprising: (i) a device substrate having a receivingsurface; (ii) a plurality of printable semiconductor elements supportedby said receiving surface; wherein each of said printable semiconductorelement comprises a semiconductor structure having a length selectedfrom the range of 0.0001 millimeters to 1000 millimeters, a widthselected from the range of 0.0001 millimeters to 1000 millimeters and athickness selected from the range of 0.00001 millimeters to 3millimeters; and (iii) a metal grid or mesh provided in electricalcontact with said plurality of printable semiconductor elementssupported by said receiving surface. In an embodiment, the printablesemiconductor element comprises a semiconductor structure having alength selected from the range of 0.02 millimeters to 30 millimeters,and a width selected from the range of 0.02 millimeters to 30millimeters, preferably for some applications a length selected from therange of 0.1 millimeters to 1 millimeter, and a width selected from therange of 0.1 millimeters to 1 millimeter, preferably for someapplications a length selected from the range of 1 millimeters to 10millimeters, and a width selected from the range of 1 millimeter to 10millimeters. In an embodiment, the printable semiconductor elementcomprises a semiconductor structure having a thickness selected from therange of 0.0003 millimeters to 0.3 millimeters, preferably for someapplications a thickness selected from the range of 0.002 millimeters to0.02 millimeters. In an embodiment, the printable semiconductor elementcomprises a semiconductor structure having a length selected from therange of 100 nanometers to 1000 microns, a width selected from the rangeof 100 nanometers to 1000 microns and a thickness selected from therange of 10 nanometers to 1000 microns.

Optionally, the printable semiconductor elements are assembled on saidreceiving surface by contact printing. Optionally, said metal grid ormesh is a laminated structure. Optionally, the metal grid or mesh isbonded to an elastomeric layer, such as a PDMS layer, and in someembodiments the elastomeric layer is bonded to a glass substrate,wherein said elastomeric layer is positioned between said metal grid ormesh and said glass substrate. Optionally, the metal grid or mesh isprovided between said receiving surface and said printable semiconductorelements. Optionally, the metal grid or mesh is provided on one or moreexternal surfaces of the printable semiconductor elements. Optionallymetal grid or mesh is optically transparent and/or has a fill factorless than 30%. Optionally, the printable semiconductor element(s)comprise a unitary, inorganic semiconductor structure.

In a system of this aspect, the printable semiconductor element(s)comprises a semiconductor structure having a length selected from therange of 0.02 millimeters to 30 millimeters, and a width selected fromthe range of 0.02 millimeters to 30 millimeters. In a system of thisaspect, the printable semiconductor element(s) comprises a semiconductorstructure having at least one longitudinal physical dimension selectedfrom the range of 0.1 millimeters to 1 millimeter. In a system of thisaspect, the printable semiconductor element(s) comprise a semiconductorstructure having at least one longitudinal physical dimension selectedfrom the range of 1 millimeters to 10 millimeters. In a system of thisaspect, the printable semiconductor element(s) comprises a semiconductorstructure having at least one cross sectional dimension selected fromthe range of 0.0003 millimeters to 0.3 millimeters. In a system of thisaspect, the printable semiconductor element(s) comprises a semiconductorstructure at least one cross sectional dimension selected from the rangeof 0.002 millimeters to 0.02 millimeters. In a system of this aspect,the printable semiconductor elements are assembled on the receivingsurface by contact printing. In a system of this aspect, the grid ormesh comprises one or more metals. In a system of this aspect, the gridor mesh is a laminated structure. In a system of this aspect, the gridor mesh is bonded to an elastomeric layer, and optionally elastomericlayer is bonded to a glass substrate, wherein the elastomeric layer ispositioned between the grid or mesh and the glass substrate, andoptionally the grid or mesh is provided between the receiving surfaceand the printable semiconductor elements. In a system of this aspect,the grid or mesh is provided on external surfaces of the printablesemiconductor elements. In a system of this aspect, the grid or mesh ismore than 50% optically transparent. In a system of this aspect, thegrid or mesh has a fill factor less than 30%.

c. Electrode Interconnect Geometries for Printable SemiconductorElements

The present invention also include electrode interconnect geometries forprintable semiconductor elements, such as printable semiconductordevices and device components, that facilitate electrode patterning andelectrical interconnection as assembly via contact printing. Theseinterconnect geometries are applicable to a range of printableelectronic devices and components thereof, including solar cells, LEDs,transistors, diodes, lasers and sensors.

In an embodiment, a printable semiconductor element of the presentinvention has a device geometry such that the contact structures, suchas contact pads or other electrical interconnection structures, formaking electrical connection are provided on a single side of theprintable semiconductor element. Preferably for some device fabricationapplications, the side of the printable semiconductor element that hasthe electrical contacts is exposed or otherwise accessible upon the stepof assembling the printable semiconductor element on a device substrate,optical system or optical component. This design is particularlyattractive for printable semiconductor elements comprising electronicdevices require two or more electrical contacts to different componentsof the device such as a solar cell, LED or transistor. In printablesemiconductor devices and device components of this aspect, the devicegeometry is selected to allow two or more electrical interconnects to beprovided on a single side of the printable semiconductor device anddevice component. In some embodiments, for example, the doping and dopedcomponents of a printable semiconductor devices and device components isselected and or spatially arranged to allow electrical interconnects tobe provided on a single side of the printable semiconductor device anddevice component.

Example 5 Contact Printing Based Assembly on Optical Components

An advantage of the contact printing-based processing methods of thepresent invention is that they are compatible with device assembly andintegration directly on a range of optical systems and opticalcomponents thereof. This allows for a range of useful structures anddevice geometries to be efficiently accessed using the presentfabrication methods.

In an embodiment of this aspect, the present invention provides a methodof making a semiconductor-based optical system comprising the steps of:(i) providing an optical system or optical component having a receivingsurface; and (ii) assembling one or more printable semiconductorelements on said receiving surface of said optical system or opticalcomponent via contact printing; wherein each of said printablesemiconductor element comprises a semiconductor structure having alength selected from the range of 0.0001 millimeters to 1000millimeters, a width selected from the range of 0.0001 millimeters to1000 millimeters and a thickness selected from the range of 0.00001millimeters to 3 millimeters. In an embodiment, the printablesemiconductor element comprises a semiconductor structure having alength selected from the range of 0.02 millimeters to 30 millimeters,and a width selected from the range of 0.02 millimeters to 30millimeters, preferably for some applications a length selected from therange of 0.1 millimeters to 1 millimeter, and a width selected from therange of 0.1 millimeters to 1 millimeter, preferably for someapplications a length selected from the range of 1 millimeters to 10millimeters, and a width selected from the range of 1 millimeter to 10millimeters. In an embodiment, the printable semiconductor elementcomprises a semiconductor structure having a thickness selected from therange of 0.0003 millimeters to 0.3 millimeters, preferably for someapplications a thickness selected from the range of 0.002 millimeters to0.02 millimeters. In an embodiment, the printable semiconductor elementcomprises a semiconductor structure having a length selected from therange of 100 nanometers to 1000 microns, a width selected from the rangeof 100 nanometers to 1000 microns and a thickness selected from therange of 10 nanometers to 1000 microns.

In some embodiments, the printable semiconductor elements are assembledon a contoured receiving surface of said optical component, such as thecurved surface(s) of a lens, lens array, waveguide or array ofwaveguides. Alternatively, the printable semiconductor elements areassembled are assembled on a planar receiving surface(s) of said opticalcomponent.

The contact printing based fabrication platform of the present methodsis highly versatile and, hence compatible with a range of opticalcomponents including light collecting optical components, lightconcentrating optical components, light diffusing optical components,light dispersing optical components, light filtering optical componentsand arrays thereof. In an embodiment, for example, printablesemiconductor elements, such as printable semiconductor based electronicdevices and/or device components, are assemble on a receiving surface ofan optical systems or component selected from the group consisting of alens, a lens array, a reflector, an array of reflectors, a waveguide, anarray of waveguides, an optical coating, an array of optical coatings,an optical filter, an array of optical filters, a fiber optic elementand an array of fiber optic elements. In an embodiment, printablesemiconductor elements are assembled on an optical component or systemfabricated by replica molding, such as a lens or lens array fabricatedby replica molding. In an embodiment, printable semiconductor elementsare assembled on a PDMS molded optical structure, such as such as a PDMSmolded lens or lens array.

Printing based assembly allows the assembled printable semiconductorelements to accurately and/or precisely spatially aligned and/orindividually addressed to features and parts of an optical system oroptical component. In an embodiment, for example, contact printingallows each of the components in an array of optical components to bespatially aligned with respect to at least one of said printablesemiconductor elements, for example aligned to within 100 microns orpreferably to within 10 microns. In an embodiment, for example, contactprinting allows each of the components in an array of optical componentsto be individually addressed to at least one of said printablesemiconductor elements.

Direct contact printing onto surfaces of optical systems and componentsenables fabrication of range of systems including display systems,photovoltaic systems, sensors, and multifunctional optical systems. Thetype and functionality of the optical system generated will depend atleast in part on the type of printable element printed and the type ofoptical system or component that receives the printable semiconductorelements. In some embodiments, the printable semiconductor elementassembled on the surface of optical systems and components areelectronic devices or components of electronic devices, such as LEDs,lasers, solar cells, sensors, diodes, transistors, and photodiodes. Insome embodiments, the printable semiconductor element assembled on thesurface of optical systems and components have thicknesses selected fromthe range of 100 nanometers to 100 microns.

Use of contact printing in the present invention provides the capable ofdirect integration of printable semiconductor elements with a range ofoptical systems. In an embodiment, for example, printable semiconductorelements are assembled on said receiving surface of an optical system oroptical component via dry transfer contact printing. Optionally,printable semiconductor elements are assembled on said receiving surfaceof an optical system or optical component using a conformable transferdevice, such as an elastomeric transfer device (e.g., PDMS stamp). In amethod of this aspect of the present comprises the steps of: (i)providing said conformable transfer device having a contact surface;(ii) establishing conformal contact between an external surface of saidprintable semiconductor element and said contact surface of saidconformable transfer device, wherein said conformal contact bonds saidprintable semiconductor element to said contact surface; (iii)contacting said printable semiconductor element bonded to said contactsurface and said receiving surface of said optical component; and (iv)separating said printable semiconductor element and said contact surfaceof said conformable transfer device, thereby assembling said printablesemiconductor element on said receiving surface of said opticalcomponent.

Example 6 Fabrication of Solar Cell Arrays Via Contact Printing

The present methods provide an effective processing platform for thefabrication of high performance photovoltaic systems including solarcell arrays.

FIG. 57 provides a process flow diagram for making printablesemiconductor elements comprising vertical solar cells that can besubsequently assembled and interconnected to fabricate a solar cellarray. Steps A-E in FIG. 57 demonstrate various processes and conditionsfor making printable solar cell ribbons from a Si (111) p-type wafer.

Process step A in FIG. 57 demonstrates processing steps and conditionsfor the back surface field formation. In this processing step, a 3 inchp-type Si 111 wafer is cleaved into 6 equal parts. Next, the processedwafer is cleaned using Ace/IPA and Piranha clean. Boron (B219) SOD isspun on and the wafer. The wafer with boron is annealed at 250° C. Theboron is driven in, for example, at 1150° C. for 45 mins. Any glassresidue is removed. These processing steps result a junction that isabout 1.5 mm thick.

Process steps B and C in FIG. 57 demonstrate processing steps andconditions for ribbon formation. A 300 nm PECVD oxide is use to make theresist pattern. The PR is patterned to define the ribbon spatialdimensions and wet etch exposed oxide with BOE. Then, ICP-DRIE ˜25-30 mmis used to generate deep trenches (12 min etch time) into the exposedsilicon. Exemplary ribbon dimensions and trench dimensions are shown inFIG. 57. The processed wafer is cleaned in RCA 1 and KOH refining forabout 4 mins to remove some of the sidewall roughness. Next, PECVD 100nm SiO₂ and 600 nm Si₃N₄ is deposited everywhere. Angled evaporation (60degree stage) of Ti/Au 3/50 nm is used in this processing step. Thewafer is exposed to RIE etching of the exposed oxide and nitride layers.Wet etching using KOH is next used to undercut the ribbons, for example,using a ˜35% KOH solution. The metal mask layers are subsequentlyremoved. The oxide and nitride layers are maintained for subsequentdoping processing.

Process steps D and E in FIG. 57 demonstrate processing steps andconditions for emitter formation. In an embodiment, a n-type dopant,such as P509, is spin coated onto the fully undercut ribbon chip. Then-type dopant (e.g., P509) is driven, for example, at 950° C. for 15mins. This creates a Junction that is about 500 nm thick. Next, thelayers are removed and transfer printed onto receiving substrates withmeshes or NOA.

FIG. 58 provides SEM images of microsolar cells of different thicknessesfabricated from bulk wafers. (Top to bottom: 8 microns, 16 microns, 22microns thick).

FIG. 59 provides a plot showing IV characteristics of an individualsolar cell device fabricated using the present processing platform. Thisexample device shows efficiency of 9%. The inset to FIG. 59 shows the Sisolar cells with a vertical geometry printed onto a bottom buselectrode.

FIG. 60 shows processing for generating top contacts for the verticalsolar cells and related electronic performance data. First, the verticalsolar cells are printed onto a Au or Cu mesh structure as shown inpanels A and B. Next, a second Au mesh is printed (laminated) on top ofthe cells and serves as the top contact. Panel C shows a plot of the IVcurve of printed contacts, modules fabricated in this way show totalefficiency of 6%. The Inset in panel C shows the top and bottom printedmesh electrodes onto the silicon solar cells.

FIG. 61 provides a schematic showing a solar cell layout of transversetype solar cells to be patterned on a <111> p-type Si wafer and capableof subsequent assembly and integration via contact printing. Thephysical dimensions of solar cell ribbons, bridge elements, trenches anda mother wafer are provided in FIG. 61. After the patterning of celllayout via photolithography and dry etching process, doping process isconducted. FIG. 62 provides a schematic showing the doping schemewherein boron (P+) and phosphorous (n+) doped regions are patterned onthe external surface of the patterned semiconductor ribbons. The topboron doping is for making top p+ contact while the top phosphorousdoping for making pn junctions. The sidewall doping strategy isimplemented purposefully to increase a junction area and to preventpossible short-circuit formation during the metallization step. Thebottom p+ doping is done for creating back-surface-field (BSF) afterundercut of bottom surface with KOH etching process.

FIG. 63 provides an overview schematic showing the process flow for cellpatterning and doping steps. As shown in FIG. 63, first the solar cellpatterns are formed on the wafer using photolithography and dry etching.Next, spatially localized boron doping is carried out for windowformation and diffusion. Next, spatially localized phosphor doping iscarried out for window formation and diffusion. Next the patterned solarcells are undercut employing top and side wall passivation and KOHetching. Finally, bottom boron doping is carried out.

FIG. 64 provides a schematic diagram showing processing steps forpatterning solar cell ribbons illustrating photolithography and STS deepRIE etching process steps. As shown in this figure, the first step inthe process flow is to make cell patterns through photolithography anddeep reactive ion etching (Bosch process) on bulk <111> Si wafer. As anetching mask, PECVD SiO₂ and positive photoresist are used. In the dryetching, SF₆ and O₂ are used for etching and C₄H₈ for passivation. As aresult of alternating etching and passivation processes in Boschprocess, the etched structure has sidewall ripples, which are smoothenout subsequently with KOH. Also shown in FIG. 64 are micrographs ofprocess wafer after removal of photoresist and SiO₂ masking layers. FIG.65 shows results from KOH refining processing of the sidewalls of thepatterned ribbons. To remove the sidewall ripples, a short time KOHrefining process is conducted. During the process, the top surface isprotected with PECVD SiO₂.

FIG. 66 provides a schematic diagram for boron doping processing. Afterthe KOH refining step, boron doping for formation of top p+ contact isconducted. PECVD SiO₂ (900 nm) is deposited as a doping mask layer and adoping window is created by photolithography and BOE wet etching. As adoping agent, either spin-on-dopant or solid state doping source can beused. The diffusion process is conducted at 1000-1150° C. under nitrogen(solid state source) or nitrogen/oxygen (75/25, spin-on-dopant)atmosphere. Also shown in FIG. 66 is a micrograph of the masked ribbonstructures having a doping window for localized boron doping. Also shownin FIG. 66 is a plot of current versus voltage indicating a 400 ohmresistance.

FIG. 67 provides a schematic diagram for phosphorous doping processing.Phosphorous doping is followed after the boron doping in order to createa shallow junction (100-300 nm). In a similar way to boron dopingprocess, phosphorous doping window is made with PECVD SiO₂ deposition,photolithography, and BOE wet-etching process. As a doping source,spin-on-dopant is used and applied by spin-coating. The diffusion isconducted at 950 C under N₂/O₂ (75/25) atmosphere. Also shown in FIG. 67is a micrograph of the masked ribbon structures for localizedphosphorous doping. Also shown in FIG. 67 is a plot of current versusvoltage indicating a 80 ohm resistance.

FIG. 68 provides a schematic diagram showing sidewall passivationprocessing. After top doping processes are finished, PECVD Si₃N₄ isdeposited as a protecting layer in KOH undercut process. To make anetching window where KOH etching starts, first, Cr and Au are depositedwith a 60° angle from the sample surface, in order to make metalprotecting layers on top and sidewalls except the bottom surface. Themetal cover surface is protected from subsequent dry etch processing,and thus functions as a passivation layer for the KOH wet-etching step.The thickness of the cells can be readily controlled by adjusting metaldeposition angle. Secondly, RIE with CHF3/O2 and SF6 will expose Si atthe bottom surface, where KOH etching can be initiated. FIG. 69 providesa schematic diagram showing processing for the formation of a KOHetching window.

FIG. 70 provides micrographs showing KOH etching processing and bottomboron doping processing. As shown in this figure, the bottom surface isetched with KOH at 90 C for 30 min, which results in print-ready cellstructure capable of assembly via contact printing, for example using anelastomeric conformable transfer device. After the KOH etching, only thebottom Si surface is exposed and the Si3N4 protecting layer can be stillused as a barrier for boron doping. Boron doping is conducted at 1000 Cfor 10 min subsequently.

After the bottom boron doping, passivation layers and remaining dopantsare cleaned out with HF, Piranha, and BOE. Before the PDMS pick-up,PECVD SiO2 can be deposited as a top-surface passivation from NOAcontamination. FIG. 71 provides images showing transfer of the solarcell ribbons from the source wafer using a PDMS transfer device.

FIG. 72 provides a schematic diagram illustrating contact printing andplanarization processing steps. Also shown in FIG. 72 are images ofprint assembled solar cells. After microcells are picked up by PDMSstamp, they are printed onto receiving substrates such as glass, PET, orKapton using NOA as an adhesive. This printing technique by itself alsocompletes the planarization of cells, which are important to make metalinterconnections. First, NOA61 is coated onto a UVO treated substrate,then microcells on PDMS are placed on top of the NOA. Due to the weightof the stamp and cells, the microcells are fully embedded in the NOAexcept the top surface where PDMS stamp is covered. After the partialcuring under UV light, the PDMS stamp can be retrieved and themicrocells are embedded and form a planar surface for followingmetallization steps.

FIG. 73 provides an imaging showing the results of metallizationprocessing. FIG. 74 provides a schematic diagram of the metallizationprocess showing an Al metal layer, SiO₂ dielectric layer, Cr/Au layer,solar cell, planarizing layer and device substrate. As shown in FIG. 73,to form metal interconnects, metals are deposited on the entire cellsurface and selective areas are etched back with metal etchant using aphotoresist or NOA as a etching protecting layer. After themetallization is implemented, those metal lines are isolated andencapsulated with SiO₂ and Al is deposited over the surface to form areflective layer. In this way, we can essentially eliminate the metalshadowing, which normally happens with conventional cell geometry.Anti-reflection coating can be further added either the bottom surfaceof the substrate or at the bottom of the cells before the transfer. Withthis cell configuration and printing strategy, we can also use theroughness of the bottom cell surface from KOH etching step as a surfacetexturization.

Example 7 Physical Dimensions of Printable Semiconductor Elements

The methods and systems of the present invention are capable ofimplementation with printable semiconductor elements, includingprintable semiconductor based devices and device components, having awide range of physical dimensions and shapes. The versatility of thepresent invention with respect to the physical dimensions and shapes ofprintable semiconductor elements assembled via contact printing enablesa wide range of device fabrication applications and accesses a widerange of electronic, optical, opto-electronic device configurations andlayouts.

FIGS. 75A and 75B provide schematic diagrams exemplifying theexpressions “lateral dimensions” and “cross sectional dimensions” asused in the present description. FIG. 75A provides a top plan view ofprintable semiconductor elements comprising 4 semiconductor ribbons6005. In the context of this description the expression “lateraldimension” is exemplified by the length 6000 and width 6010 of thesemiconductor ribbons 6005. FIG. 75B provides a cross sectional view ofthe printable semiconductor elements comprising 4 semiconductor ribbons6005. In the context of this description the expression “cross sectionaldimension” is exemplified by the thickness 6015 of the semiconductorribbons 6005.

In some embodiments, one or more of the lateral dimensions, such aslengths and widths, of the printable semiconductor elements, includingprintable semiconductor based devices and device components, areselected over the range of 0.1 mm to 10 mm. One or more of the lateraldimensions are selected over the range of 0.1 mm to 1 mm for someapplications, and selected over the range of 1 mm to 10 mm for someapplications. Use of printable semiconductor elements having theselateral dimensions include, but are not limited to, membrane solar cellsand photovoltaic systems thereof.

In some embodiments, one or more of the lateral dimensions, such aslengths and widths, of the printable semiconductor elements, includingprintable semiconductor based devices and device components, areselected over the range of 0.02 mm to 30 mm. Use of printablesemiconductor elements having these lateral dimensions include, but arenot limited to, optoelectronic semiconductor elements and systemsthereof.

In some embodiments, one or more of the lateral dimensions, such aslengths and widths, of the printable semiconductor elements, includingprintable semiconductor based devices and device components, areselected over the range of 0.0001 mm to 1000 mm. One or more of thelateral dimensions, such as lengths and widths, are preferably selectedover the range of 0.0001 mm to 300 mm for some applications

In some embodiments, one or more of the cross sectional dimensions, suchas thicknesses, of the printable semiconductor elements, includingprintable semiconductor based devices and device components, areselected over the range of 0.002 mm to 0.02 mm. One or more of the crosssectional dimensions, such as thicknesses, of the printablesemiconductor elements, including printable semiconductor based devicesand device components are selected over the range of 0.0003 mm to 0.3 mmfor some applications. One or more of the cross sectional dimensions,such as thicknesses, of the printable semiconductor elements, includingprintable semiconductor based devices and device components are selectedover the range of 0.00001 mm to 3 mm for some applications.

In an optical system of the present invention, the printablesemiconductor element comprises a semiconductor structure having alength selected from the range of 0.02 millimeters to 30 millimeters,and a width selected from the range of 0.02 millimeters to 30millimeters. In an optical system of the present invention, theprintable semiconductor element comprises a semiconductor structurehaving a length selected from the range of 0.1 millimeters to 1millimeter, and a width selected from the range of 0.1 millimeters to 1millimeter. In an optical system of the present invention, the printablesemiconductor element comprises a semiconductor structure having alength selected from the range of 1 millimeters to 10 millimeters, and awidth selected from the range of 1 millimeter to 10 millimeters. In anoptical system of the present invention, the printable semiconductorelement comprises a semiconductor structure having a thickness selectedfrom the range of 0.0003 millimeters to 0.3 millimeters. In an opticalsystem of the present invention, the printable semiconductor elementcomprises a semiconductor structure having a thickness selected from therange of 0.002 millimeters to 0.02 millimeters. In an optical system ofthe present invention, the printable semiconductor element has at leastone longitudinal physical dimension less than or equal to 200 microns.In an optical system of the present invention, the printablesemiconductor element has at least one cross-sectional physicaldimension selected over the range of 10 nanometers to 10 microns.

The present invention includes optical system comprising a plurality ofprintable semiconductor elements, such as printable electronic devicesor device components, assembled via contact printing. In embodimentpresent invention, for example, the optical system further comprises aplurality of printable semiconductor elements on said receiving surfaceof said substrate via contact printing; wherein each of said printablesemiconductor elements comprises a semiconductor structure having alength selected from the range of 0.0001 millimeters to 1000millimeters, a width selected from the range of 0.0001 millimeters to1000 millimeters and a thickness selected from the range of 0.00001millimeters to 3 millimeters.

Example 8 Printable GaAs/InGaAlP Red LEDs Printed on PET Substrates

FIG. 76 shows an array of printable GaAs/InGaAlP red LEDs printed on PETsubstrates. To form the device, PET substrates are coated with a thin(1-2 micron) layer of PDMS, the PDMS is cured thermally, and an array ofsparse gold meshes is printed onto the substrate via contact printing. 1mm×1 mm×˜0.3 mm LEDs are then contact printed onto the mesh electrodes.After printing the LEDs, a thin PDMS substrate housing another array ofmeshes is laminated against the substrate to form electrical contact tothe top of the LEDs and allow operation at ˜5 V (top left and right).The thin PDMS substrate also serves as mechanical encapsulation of theLED array

STATEMENTS REGARDING INCORPORATION BY REFERENCE AND VARIATIONS

U.S. patent application Ser. Nos. 11/115,954, 11/145,574, 11/145,542,60/863,248, 11/465,317, 11/423,287, 11/423,192, and Ser. No. 11/421,654are hereby incorporated by reference to the extent not inconsistent withthe present description.

All references throughout this application, for example patent documentsincluding issued or granted patents or equivalents; patent applicationpublications; and non-patent literature documents or other sourcematerial; are hereby incorporated by reference herein in theirentireties, as though individually incorporated by reference, to theextent each reference is at least partially not inconsistent with thedisclosure in this application (for example, a reference that ispartially inconsistent is incorporated by reference except for thepartially inconsistent portion of the reference).

The terms and expressions which have been employed herein are used asterms of description and not of limitation, and there is no intention inthe use of such terms and expressions of excluding any equivalents ofthe features shown and described or portions thereof, but it isrecognized that various modifications are possible within the scope ofthe invention claimed. Thus, it should be understood that although thepresent invention has been specifically disclosed by preferredembodiments, exemplary embodiments and optional features, modificationand variation of the concepts herein disclosed may be resorted to bythose skilled in the art, and that such modifications and variations areconsidered to be within the scope of this invention as defined by theappended claims. The specific embodiments provided herein are examplesof useful embodiments of the present invention and it will be apparentto one skilled in the art that the present invention may be carried outusing a large number of variations of the devices, device components,methods steps set forth in the present description. As will be obviousto one of skill in the art, methods and devices useful for the presentmethods can include a large number of optional composition andprocessing elements and steps.

Every formulation or combination of components described or exemplifiedherein can be used to practice the invention, unless otherwise stated.

Whenever a range is given in the specification, for example, atemperature range, a time range, or a composition or concentrationrange, all intermediate ranges and subranges, as well as all individualvalues included in the ranges given are intended to be included in thedisclosure. It will be understood that any subranges or individualvalues in a range or subrange that are included in the descriptionherein can be excluded from the claims herein.

All patents and publications mentioned in the specification areindicative of the levels of skill of those skilled in the art to whichthe invention pertains. References cited herein are incorporated byreference herein in their entirety to indicate the state of the art asof their publication or filing date and it is intended that thisinformation can be employed herein, if needed, to exclude specificembodiments that are in the prior art. For example, when composition ofmatter are claimed, it should be understood that compounds known andavailable in the art prior to Applicant's invention, including compoundsfor which an enabling disclosure is provided in the references citedherein, are not intended to be included in the composition of matterclaims herein.

As used herein, “comprising” is synonymous with “including,”“containing,” or “characterized by,” and is inclusive or open-ended anddoes not exclude additional, unrecited elements or method steps. As usedherein, “consisting of” excludes any element, step, or ingredient notspecified in the claim element. As used herein, “consisting essentiallyof” does not exclude materials or steps that do not materially affectthe basic and novel characteristics of the claim. In each instanceherein any of the terms “comprising”, “consisting essentially of” and“consisting of” may be replaced with either of the other two terms. Theinvention illustratively described herein suitably may be practiced inthe absence of any element or elements, limitation or limitations whichis not specifically disclosed herein.

One of ordinary skill in the art will appreciate that startingmaterials, biological materials, reagents, synthetic methods,purification methods, analytical methods, assay methods, and biologicalmethods other than those specifically exemplified can be employed in thepractice of the invention without resort to undue experimentation. Allart-known functional equivalents, of any such materials and methods areintended to be included in this invention. The terms and expressionswhich have been employed are used as terms of description and not oflimitation, and there is no intention that in the use of such terms andexpressions of excluding any equivalents of the features shown anddescribed or portions thereof, but it is recognized that variousmodifications are possible within the scope of the invention claimed.Thus, it should be understood that although the present invention hasbeen specifically disclosed by preferred embodiments and optionalfeatures, modification and variation of the concepts herein disclosedmay be resorted to by those skilled in the art, and that suchmodifications and variations are considered to be within the scope ofthis invention as defined by the appended claims.

1. (canceled)
 2. A method of making an integrated optical devicecomprising the steps of: transfer printing a plurality of printablesemiconductor elements to a device substrate; and addressing an opticalcomponent or an array of optical components with the plurality ofprintable semiconductor elements on the device substrate, wherein eachof the plurality of printable semiconductor elements are opticallyaddressed to the optical component or to a unique individual member ofthe array of optical components.
 3. The method of claim 2 for making anintegrated solar cell and microlens array, wherein the transfer printingcomprises the steps of: contacting an array of solar cells on a waferwith a stamp contact surface; removing the stamp in a direction awayfrom the wafer to transfer the array of solar cells from the wafer tothe stamp contract surface; transferring the array of solar cells fromthe stamp contact surface to a back electrode supported by a targetassembly substrate; wherein the method further comprises the steps of:providing an insulating layer and front electrodes in electrical contactwith the transferred array of solar cells; and addressing an array ofmicrolenses with the transferred array of solar cells, wherein eachmicrolens in the array is individually addressed and optically alignedwith an individual solar cell.
 4. The method of claim 3, wherein thearray of microlenses is a molded array of microlenses.
 5. The method ofclaim 3, wherein the microlenses comprise concentrating lenses to focusincident light on a solar cell to which the microlens is individuallyaddressed.
 6. The method of claim 3, wherein the solar cells are amultilayer structure comprising: an antireflection layer; a top contactthat traverses the antireflection layer; a p-n junction in electricalcontact with the top contact; and a bottom layer that supports the p-njunction.
 7. The method of claim 3, wherein the microlenses comprisecollectors to optically focus light to solar cells, wherein eachmicrolens—solar cell individually addressed pair has a collector area tosolar cell area ratio that is greater than or equal to
 400. 8. Themethod of claim 7, wherein the collectors have an individual size thatis about 2 mm and the solar cells have an individual size that is about0.1 mm.
 9. The method of claim 3, wherein the array of microlenses ismade by replica molding.
 10. The method of claim 9, wherein the array ofmicrolenses comprises a plano-concave polymer lens array.
 11. The methodof claim 3, wherein the array of microlenses comprises Fresnel lenses.12. The method of claim 3, wherein the array of microlenses comprisehorizontal light pipes, waveguides, or both horizontal light pipes andwaveguides.
 13. The method of claim 3, wherein the solar cells comprisesilicon solar cells made from a silicon on insulator wafer.
 14. Themethod of claim 3, wherein the solar cell comprises a doped top surfacewith a P/As mixture supported by a buried oxide layer.
 15. The method ofclaim 3, further comprising the steps of: casting the insulating layeron the printed solar cells, thereby planarizing the printed solar cells;and depositing the top electrodes on the planarized printed solar cells.16. The method of claim 3, wherein the stamp is an elastomeric stamp.17. The method of claim 3, wherein the front electrodes are aligned in adirection that is perpendicular to the transferred array of solar cellsto minimize shadowing of solar cells by the front electrodes.
 18. Themethod of claim 17, wherein the front electrodes optically obstruct alateral distance of an underlying solar cell, wherein the opticallyobstructed lateral distance is less than 60 μm for a solar cell having alength greater than about 1 mm.
 19. The method of claim 3, wherein atleast 1000 micro solar cells are transfer printed in parallel.
 20. Themethod of claim 2, wherein the plurality of printable semiconductorelements are part of: a light emitting diode (LED) addressed to adiffusing optical lens; a vertical-cavity surface-emitting laser (VCSEL)addressed to an optical fiber; a solar cell addressed to a collectingoptical lens; a photodiode addressed to a collecting optical lens; or anoptical sensor and an optical generator addressed to a collecting lens.21. The method of claim 2, wherein the device substrate is a thin andflexible substrate and the transferred semiconductor elements are partof an LED having a thickness less than or equal to 0.3 mm and greaterthan or equal to 0.0003 mm to provide a conformable LED lighting system.22. A semiconductor-based optical system comprising: a device substrate;a plurality of device components supported by the device substrate,wherein each device component comprises a printable semiconductorelement; and an array of optical components, wherein each member of thearray of optical components is optically addressed to a unique member ofthe plurality of device components.
 23. The semiconductor-based opticalsystem of claim 22, wherein: the device components comprise micro-solarcells and the optical components comprise a collecting optical lensconfigured; and the array of collecting optical lens concentrate lighton the solar cells.
 24. The semiconductor-based optical system of claim23, wherein each collecting optical lens has a collector area and eachmicro-solar cell has a solar cell area, and the ratio of collector areato solar cell area is greater than or equal to
 400. 25. Thesemiconductor-based optical system of claim 22, wherein the opticalcomponents comprise a polymer lens array.